N A S A T E C H N I C A L

REPORT

F
a
m
2
L

VIBRATION-TRANSLATION
ENERGY TRANSFER IN
VIBRATIONALLY EXCITED
DIATOMIC MOLECULES .. "

-.
I *
.
" '
; .
Robert
Lawrence
McKenzie 8 ,,
..

A m e s ResearchCenter

NATIONAL
AERONAUTICS
AND
SPACE
ADMINISTRATION WASHINGTON, D. C. OCTOBER 1976 ,
 -

TECH LIBRARY KAFB, NM

00b857b
1. Reput No. 2. GovsmmentAccession No. 3. Recipient'sCatalogNo.
NASA TR R-.466
4. Title and Subtitle 5. Report Date
VIBRATION-TRANSLATION ENERGY TRANSFER IN VIBRATIONALLY October 1976
EXCITED DIATOMIC MOLECULES 6. PerformingOrganizationCode

~~

7. Author(s1 8. PerformingOrganization Report No.

Robert Lawrence McKenzie A-6453

9. Performing Organization Name and Addrcu

Ames Research Center 11.ContractorGrant No.

Moffett Field, Calif. 94035

13. Type of Report andPeriodCovered

12. SponsoringAgencyNameandAddress Technical Report
National Aeronautics and Space Administration I-
14. SponsoringAgency Code
Washington, D. C. 20546

16.Abstract

A semiclassical collision model is applied to the study of energy transfer rates between a
is modeled as an
vibrationally excited diatomic molecule and a structureless atom. The molecule
anharmonic oscillator with a multitude of dynamically coupled vibrational states. Three main
aspects in the prediction of vibrational energy transfer rates are considered. The applicability
of the semiclassical model to an anharmonic oscillator is first evaluated for collinear encounters.
Second, the collinear semiclassical model is applied to obtain numerical predictions of the vibra-
tional energy transfer rate dependence
on the initial vibrational state quantum number. Thermally
averaged vibration-translation rate coefficients are predicted and compared with CO-He experimental
values for both ground and excited initial states. The numerical ismodel
also used as a basis for
evaluating several less complete but analytic models. Third, the role of rotational motion in the
dynamics of vibrational energy transfer is examined. A three-dimensional semiclassical collision
model is constructed with coupled rotational motion included. Energy transfer within the molecule
is shown to be dominated by vibration-rotation transitions with small changes in angular momentum.
The rates of vibrational energy transfer in molecules with rotational frequencies that are very
small in comparison to their vibrational frequency are shown to be adequately treated by the prece
collinear models.

7. Key Words(Suggested by Author(r)) 18.DistributionStatement

Diatomic molecules
Vibrational relaxation rates
Vibration-totation energy transfer Unlimited
Semiclassical collision models
STAR Category- 72
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 .

TABLE OF CONTENTS

Page

1. Introduction ........................... 1
1.1 New Aspects in Modern Vibrational Relaxation Processes. . . . 1
1.2 Role of Vibration-Translation Energy Transfer ........ 4
1.3 Purpose and Objectives of This Study ............. 6
1.4 Overview of the Contents and Results ............. 10

.
2 Concepts in Vibrational Energy Transfer ............. 15

.. . . . . . .
2.1 Historical S u m m a r y and Review Literature Guide 15
2.2 General Considerations . . . . . . . . . . . . . . . . . . . 21
2.2.1 Modes of Energy Transferin Diatomic Molecules . . . . 21
2.2.2 Rate Coefficients from the Collision Dynamics. . . . 24
2.2.3 Controlling Variables in Vibrational Energy Transfer 26
2.3 Theoretical Methods for Modeling Collision Dynamics .... 28
2.3.1 Classical Collision Theories ............. 29
2.3.2 Quantum-Mechanical Theories . . . . . . . . . . . . . 30
2.3.3 Semiclassical Collision Model . . . . . . . . . . . . 32
2.4 Basic Criteria for the Semiclassical Approximation..... ' 33

3 . Intramolecular and Collision-Interaction Potentials ........ 37

3.1 Intramolecular Potential . . . . . . . . . . . . . . . . . . . 37

3.1.1 Vibrational fmharmonicity ............... 37

3.1.2Vibration-RotationCoupling .............. 41

iii

...
 3C
. 2o l l i s i o n - I n t e r a c t i oPno t e n t i a l ............... 45

3 . 2S. 1p h e r i cFael a t u r e s .................. 47

3.2.2Anisotropic Features ................. 51

3.2.3 Three-Dimensional Interaction Potential Model . . . . 53

3 . 2 .C 4 o l l i n e aI rn t e r a c t i oPno t e n t i a l Model . . . . . . . . 55

4 . A ComparativeEvaluation of theSemiclassicalApproximation .. 57
4 . 1S e m i c l a s s i c a l Model f o rC o l l i n e a rC o l l i s i o n s ........ 59
4 . 1 . 1I n c i d e n tP a r t i c l eM o t i o n .............. 61
4.1.2 Oscillator Motion ................. 63

4.1.3Coupling of t h eO s c i l l a t o rM o t i o na n dt h e Classical

Trajectory ..................... 65

4 . 1 . 4F i r s t - o r d e rP e r t u r b a t i o nS o l u t i o n s ......... 65

4.1.5NumericalSolutionMethods ............. 67
4.2 A ComparisonwithFullyQuantuwMechanicalSolutions ... 68

4.2.1EnergyConservationandthe Classical Parameters .. 68

4 . 2 . 2I n f l u e n c e of O s c i l l a t o rR e s p o n s e on t h e Classical

Motion ....................... 74

4 . 2 . 3A p p l i c a b i l i t y of t h eF i r s t - O r d e rP e r t u r b a t i o nT h e o r y 77

4.3 Summary .......................... 78

5 . V i b r a t i o n a l Quantum
Number Dependence of Energy T r a n s f e r Rates .. 81

5.1 C o l l i s i o n Model ....................... 82

5 . 1 . 1F e a t u r e sI n f l u e n c i n gt h eE x c i t e d - S t a t eC o l l i s i o n

Dynamics ....................... 82

5.1.2
Aspects of t h e Semiclassical Numerical Model . . . . . 85

iv
 5.1.3 Thermally Averaged Rate Coefficients from a Collinear

Semiclassical Model.................. 87

5.2AnalyticApproximations ................... 89

5.2.1 Keck-Carrier Formula for Anharmonic Oscillators . . . . 90

5.2.2 Mies Perturbation Solution for Anharmonic Oscillators . 91

5.2.3 Kerner Solution for Linearly-Forced Harmonic

Oscillators ...................... 93

5.3 Comparisons with CO-He Experiments . . . . . . . . . . . . . . 95

5.3.1 Effective Interaction Potential Parameters ...... 96

5.3.2 Comparisons with Excited-State Rate Measurements . . . 98

5.4 An Evaluation of the Analytic Approximations. . . . . . . . . 99

5.5 Multiple-Quantum Transitions . . . . . . . . . . . . . . . . . 104

5.6 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . 107

.
6 111
Effects of Rotational Transitions on Vibrational Energy Transfer ..
6.1 Vibration-Rotation Collision Model . . . . . . . . . . . . . . 112

6.1.1 Interaction Potential . . . . . . . . . . . . . . . . . 113

6.1.2 Quantized Molecular Dynamics . . . . . . . . . . . . . 114

6.1.2.1 Radial Matrix Elements . . . . . . . . . . . . 117

6.1.2.2 Spherical Matrix Elements . . . . . . . . . . 119

6.1.2.3 Complete Factored Matrix Elements . . . . . . 120
6.1.3 Classical Trajectory . . . . . . . . . . . . . . . . . 126
6.2 Representations of the Results . . . . . . . . . . . . . . . . 131
6.3 Numerical Methods of Solution . . . . . . . . . . . . . . . . 134

V
 6.4 Effective Hamiltonian and Other Approximations . . . . . . . . 136
6.4.1 Sudden-RotatiodPerturbed-Vibration Approximation . . . 136
6.4.2 Maximum Coupling Approximation . . . . . . . . . . . . .137
6.4.3 Effective Hamiltonian . . . . . . . . . . . . . . . . . 138
6.5 Aspects of Convergence . . . . . . . . . . . . . . . . . . . . 140
6.5.1 Evaluation of the Projection-State Decoupling

. . Approximations .................... 141

6.5.2 Convergence Requirements for Vibration-Rotation Energy

Transfer ....................... 144

6.6 Ambiguities of Unconserved Energy in
a Three-Dimensional

Semiclassical Model ..................... 151

6.7 Three-dimensional Inelastic Collisions and Their Relation to

Collinear Encounters ..................... 154

6.7.1 H,- He Collisions . . . . . . . . . . . . . . . . . . . 156
6.7.2 N,- He Collisions . . . . . . . . . . . . . . . . . . . 161

6.7.3 CO-He Collisions ................... 171

6.8 Classification of Rotational Coupling Effects on Vibrational

Energy Transfer ....................... 173

.
7 A Review and Some Considerations for Future Study ......... 177

7.1 Review of the Newfound Aspects of Vibrational Energy

...........................
Transfer 177

7.2 Considerations for Future Study ............... 182

vi
 APPENDIX

A. .............................
Notation 185

B. General Formulation of the Semiclassical Collision Theory. . . . 189

B.l Classical Trajectory .................... 190

B.2 Quantum-Mechanical Molecular Motion . . . . . . . . . . . . . 192

B . 3 First-Order Perturbation Theory. . . . . . . . . . . . . . . 196

C . Radial Matrix Element Integral. . . . . . . . . . . . . . . . . . 199

D . Spherical Matrix Element Integral . . . . . . . . . . . . . . . . 209

E . Analytic Trajectory Equations for Nonzero Impact Parameter .... 215

F . Symmetries of Vibration-Rotation Matrix Elements and Their

Compact Computer Storage ..................... 219

F.l Symmetries of V v’R’m’vRm . . . . . . . . . . . . . . . . . . 222

F.l.lExchangeSymmetry .................. 224

F .1 . 2 Projection-State Sign-Reversal Symmetry . . . . . . . 224

F.2 Primary Matrix Element Storage . . . . . . . . . . . . . . . 225

References ............................. 229

vii

. . .
 VIBRATION-TRANSLATION ENERGY TRANSFER IN VIBRATIONALLY

EXCITED DIATOMIC MOLECULES

Robert Lawrence McKenzie

Ames Research Center

CHAPTER I

INTRODUCTION

1.1 New Aspects in Modern Vibrational Relaxation Processes

While the collisional excitation of vibrations in diatomic molecules has

been a frequently studied topic for 1-4 an

decades, increasing interest in

processes that depend on the details of energy transfer to specific vibra-

tional states has put new demands on the analysis of such collisions. The

following comparison of the early class of relaxation processes with those

introduced in the past decade demonstrates the new features required

a in

theoretical model of vibrational energy transfer.

Early studies of vibrational relaxation in gases were concerned mainly

with the influence of vibrational energy transfer on the bulk thermodynamic

properties during the relaxation process. Phenomena such as the absorption

and dispersion of ultrasonic waves5r6 or the vibrational excitation behind

shock waves7r8 were described analytically in terms of an effective "relaxa-

tion time," T, that characterized the rate at which the collisional exchange

of vibrational and translational energies brought the total energy in vibra-

tions toward equilibrium. Only a single relaxation equation was then

necessary, in the simple form:

*Submitted to York University as partial fulfillment of Ph.D.,1976.

April
,
S
1
 dev e; -
” -
dt T

where e, is the total specific energy in vibrations and e$ is the corre-

sponding value at thermodynamic equilibrium with the local stategas

of the

(see Appendix A for a list

of symbols). The factors controlling these early

(1.1) (e.g.,
processes are evident in the derivation leading to equation

Vincenti and Kruger, Ch. 7 ) . The gas is considered to be an admixture of

harmonic oscillators in a thermal heat bath of structureless inert atoms. T

harmonic oscillator quantal properties allow only single-quantum transitions

and lead to the Landau-Teller4 relationship describing the quantum number

dependence of rate coefficients:

kv,v- 1 = vk 190 (1.2)

denotes the rate coefficient for transitions from oscillator

v-1 induced by oscillator-atom collisions. A set of simplified

rate equations describing the detailed kinetics can then be collected into

simple equation from which the parameter,

T, emerges in the form

-hw/kT
T = [(l - (e1.3) >kl,,-p/ml-’

where w is the fundamental oscillator frequency andT, p, and m are the

kinetic temperature, density, and average molecular mass of the gas mixtur

respectively. Equations (1.1) and (1.3) combine to illustrate the principal

common featureof processes described this way; viz, the only collision param-

eter required is the rate of single-quantum transitions to the ground state.

The descriptionis independent of the population distributions among higher

In
vibrational states andno assumptions regarding their definition is made.

a more detailed account of the kinetics that includes the exchange of vibr

tional energy between oscillators, Montroll and Shulerg show that a populat
2
distribution of harmonic oscillator states rapidly recovers from an arbitrary

distortion and achieves

a Boltzmann distribution described by some nonequilib-

rium "vibrational temperature." The recovery occurs aintime period small

compared to T, causing the subsequent relaxation to proceed through

a contin-

uous sequenceof Boltzmann distributions. This result further reduced any

concern for the details of energy transfer to excited vibrational states

beyond the description given by equation (1.2).

As experimental studies of vibrational relaxation became more detailed,

the kinetic models based on harmonic oscillator properties appeared less

- . ..
capable of describing the observations. Motivated by some large discrepancies

between theory and experiment in nonequilibrium supersonic expansions,

the anharmonicity of most

Treanor, Rich, and Rehm" recently showed that small

diatomic molecules was sufficient to generate non-Boltzmann distributions

among upper vibrational states during some relaxation processes. The impor-

tance of oscillator anharmonicity in the vibrational kinetics has since been

amplified by the introduction

of infrared gas lasers,
11-15 where the effects

to produce the necessary population inversions

of anharmonicity are essential

among vibration-rotation states.

l3 Some recent proposals using lasers
to

selectively excite specific vibrational states for photochemical or isotope

separation experiments will also be strongly influenced by the ofeffects

anharmonicity. These modern applications of vibrational nonequilibrium con-

stitute a new class of relaxation processes that depend on of dis-

the degree

tortion froma Boltzmann population distribution. Their analysis requires

a

- one for each contribut-

detailed solution to the set of relaxation equations

- that describes the change in number density, Nv, of

ing vibrational state

each state v. A general form of the relaxation equations can be written as

3
 "
dNV
dt = cc
i v'
kv',v N iNv'

where Ni denotes the number density of all species or states

i and
kvl ,v
is the rate coefficient for transitions from state
v' to v. Equation (1.2)

of k,'
is not an accurate description of the quantum number dependence
,v
when the oscillator is anharmonic, and the selection rule allowing only

single-quantum transitions is also invalid. Thus the simplifications of

equation (1.4) leading to equation(1.1) and the concept of an effective

relaxation time given by equation (1.3) are no longer applicable. Rate coeffi-

cients for transitions from excited vibrational states are as essential to

analysis of such processes as

k l Y 0 is and vibrational anharmonicity will have

a major influence on their values. Since this study is concerned mainly with

the rate of energy transfer to excited states, oscillator anharmonicity is

therefore a basic feature to be included.

1.2 Role of Vibration-Translation Energy Transfer

In most modern applications involving vibrational nonequilibrium and

particularly in the analysis of infrared gas lasers, the collisional exchang

of vibrational and translational energies must usually be consideredof as one

several paths for energy transfer to the molecular state in question.

As

equation (1.2) indicates, the rate of vibration-translation (V-T) energy

transfer increases with quantum number even in the simplest model of the

oscillator. Thus, the V-T process can dominate the flow of energy from upper

vibrational levels even where it may be insignificant to the kinetics of

levels. In some cases, it may provide the principal path for vibrational

energy loss from the system. An essential feature of the V-T rates is there-

fore their dependence on the initial state quantum number, particularly in

4
deexcitation processes where excess vibrational energy has been produced.

Unfortunately, very l i t t l e quantitative information defining the quantum num-

berdependenceof V-T rates f o r even the simplest diatomic molecules is

presently available from e i t h e r e x p e r i m e n t o r t h e o r y .

Experimental ground-state excitation rates have been obtained from mea-

surements behind shock waves16 o r i n f l u o r e s c e n c e e x p e r i m e n t s 1 ’ f o r many y e a r s

by d e t e r m i n i n gt h ev a l u eo f T i n equation (1.1) t h a tb e s tf i t st h eo b s e r v a -

tions. However, t h e d i f f i c u l t y o f o b t a i n i n g e x p e r i m e n t a l V-T rates f o r mole-

cules i n well-defined excited vibrational states is i n d i c a t e d by t h e s p a r s i t y

ofattempts. Numerous experimentershaverecentlymeasuredthe rates of

v i b r a t i o n - v i b r a t i o n (V-V) e n e r g y e x c h a n g e b e t w e e n p a i r s o f o s c i l l a t o r s i n

excited statesl8,lg becausethefast V-V transfercaneasilybe made a dominant

mechanism; b u tt od a t e ,o n l yo n ec o m p r e h e n s i v e set of upper-level V-T rate

measurementshasbeenreported. l8 Even then,whiletheexperiment was cleverly

designedandcarefullyanalyzed,theconditions were complexand t h e measure-

ments r e q u i r e d s u b s t a n t i a l c o r r e c t i o n t o c o m p e n s a t e f o r e x t r a n e o u s modes of

energytransfer.

Theoreticalstudiesaddressedtotheanalysis of i n i t i a l l y e x c i t e d o s c i l -

l a t o r sh a v eb e e ns i m i l a r l y sparse. S i n c et h er e l a x a t i o n t i m e , T , is deter-

mined s o l e l y by t h e rate o f s i n g l e - q u a n t u m t r a n s i t i o n s t o t h e g r o u n d state,

kl,O, t h e u s u a l t h e o r e t i c a l a p p r o a c h h a s c e n t e r e d on a h a r m o n i c o s c i l l a t o r

model o f t h e m o l e c u l e i n i t i a l l y i n t h e ground s t a t e . The small-amplitude

oscillations characteristic of t h e ground s t a t e t h e n a l l o w a linearized inter-

action potential between the oscillator andan incident particle to be used.

By a s s u m i n g f u r t h e r t h a t t h e p a r t i c l e t r a j e c t o r y is collinear with the molecu-

l a r a x i s andby adopting a semiclassicalapproximation,thelinearized

5
interaction makes possible an exact and convenient analytical solution for

oscillator transition probabilities for any initial state. However, the

inaccuracy of the harmonic oscillator model has been demonstrated by Mies

even for .transitions originating from the ground state. Mies found that the

use of an anharmonic oscillator potential introduces matrix elements associ

with oscillator transitions that are no longer equal on the diagonal.

(A har-

monic oscillator with an interaction linear in the oscillator coordinate h

constant diagonal matrix elements.) The nonzero differences

in the diagonal

matrix elements introduce additional phase differences between the time-

dependent oscillator eigenfunctions during a collision and can lead to lar

corrections to the harmonic oscillator model. Because the origin of these

corrections resides in the unperturbed oscillator eigenfunctions (from which

the matrix elements are computed), their effects are not always reproduced by

the popular practice of simply inserting oscillator eigenenergies, corrected

for anharmonicity, into a harmonic oscillator theory. Nevertheless, in the

absence of better analytic solutions, such theoretical models are frequent

used to predict the quantum number dependence of V-T 11-15

rates.Thus, a need

clearly exists for the development of a suitable analytic solution containin

anharmonicity as a fundamental feature.

1.3 Purpose and Objectives of This Study

While the modern literature is abound with comprehensive and detailed

studies of the collisional excitation of diatomic molecules in vibration and

rotation (see almost any recent issue of the Journal of Chemical Physics),

vibrational states higher than the second are rarely considered. The objec-

tives are usually either to examine improved techniques for calculating the

collision dynamics or
to obtain a quantitatively accurate estimate of the

6
inelastic cross sections. The collision models used in the latter case are

usually fully quantum mechanical and hence are as exact asof the
the form

interaction potential chosen for study. These studies are clearly

a necessary

step in the understanding of molecular collision dynamics since they provide

the most precise test of our ability to explain the experimental observations

Unfortunately, the computational requirements to obtain such precision are

of such studies. To a pragmatist con-

expensive and tend to limit the scope

cerned with the analysis a of

mdern macroscopic process, these studies of

microscopic collision dynamics are seldom able to provide much useful informa

tion about the thermally averaged rate coefficients for molecules in excited

states. Furthermore, even if exact calculations were typically carried far

enough to produce rate coefficients,

a means of numerically reproducing the

results inexpensively would be required before they could be conveniently

applied ina solution of the macroscopic rate equations. This study

is

addressed to the pragmatist and to four corresponding objectives.

The first objectiveis to examine the inelastic collision dynamics of

diatomic molecules in an arbitrary initial state struck

a structureless
by

of such encounters
atom. The purpose is to explore the qualitative features

and to identify the parameters and physical features contributing most to the

prediction of the associated energy-transfer rates. By including

a complete

account of the coupling between interacting vibrational states, especially as

it is amplified by anharmonicity, the results provide

a basis for evaluating

of the collision process that may have emphasis

more approximate treatments on

other'aspects, such as those with sufficient simplifications to allow analyt

solution or those including coupled rotational motion.

7
 A secondobjectiveofthisstudy i s t o e v a l u a t e several a n a l y t i c c o l l i -

sion models in popular use for predicting the quantum number dependenceof V-T

rate c o e f f i c i e n t s . This o b j e c t i v e i s motivatedbytheimportanceofhavingan

i n e x p e n s i v en e a n so fg e n e r a t i n gv a l u e so fk v Y V ' when s o l v i n gt h ed e t a i l e d

rate e q u a t i o n s t y p i f i e d by e q u a t i o n (1.4). A c o l l i s i o n model w i t h s u f f i c i e n t

generality to be applicable for all conditions of interest in modern a p p l i c a -

t i o n s w i l l necessarilyrequirenumericalsolution,andthefirstobjectives of

t h i ss t u d y are m e t o n l yw i t hs u c h a model. The s o l u t i o n s are time consuming,

however,andwould be prohibitively expensive in a practical application.

C o n s e q u e n t l y ,t h eu s u a lp r a c t i c e i s t o o b t a i n a s i m p l ea n a l y t i ca p p r o x i m a t i o n

by i n t r o d u c i n g s u f f i c i e n t a s s u m p t i o n s t o d e c o u p l e t h e i n t e r a c t i o n s b e t w e e n

o s c i l l a t o r states and t o l i n e a r i z e t h e i n t e r a c t i o n b e t w e e n t h e o s c i l l a t o r a n d

i t s c o l l i s i o np a r t n e r . Several s u c hs o l u t i o n sh a v eb e e ne x t r a c t e d ,b u tt h e y

a l l exclude one or more p r o p e r t i e s o f t h e c o l l i s i o n p r o c e s s t h a t r e m a i n impor-

tantin a g e n e r a l i z e d model. L i t t l e d e f i n i t i o n ,i fa n y ,o ft h er a n g eo f

applicability of these analytic solutions appears in the literature in other

t h a nt h e most g e n e r a l terms. The s e c o n do b j e c t i v ed e s c r i b e dh e r e i s a ne f f o r t

t o d e f i n e more e x p l i c i t l y t h e i r r a n g e of a p p l i c a b i l i t y f o r p r e d i c t i n g e x c i t e d -

state rate c o e f f i c i e n t s .

A thirdobjective of this study i s toevaluatetheconsequenceof

severalsimpli'fyingassumptionsregardingtheequations of motionandthecol-

l i s i o n geometry t h a t were n e c e s s a r y t o meet t h e p r e c e d i n g o b j e c t i v e s . A fun-

damentalsimplificationtotheequationsofmotion i s achievedherebyadopt-

ing a semiclassicalor"impact parameter'' d e s c r i p t i o n o f t h e c o l l i s i o n

dynamics. 2 2 - 2 3 The p a t h of t h e i n c i d e n t p a r t i c l e i s o b t a i n e dc l a s s i c a l l y ,

w h i l et h eo s c i l l a t o rr e s p o n s e i s t r e a t e d quantummechanically. As a result,

8
the second-order quantum mechanical equation of motion
is reduced to two first-

order differential equations, that are subsequently decoupled. The complexity

of solution is thereby reduced greatly. However, the semiclassical approxima-

tion failsto properly account for the quantal interference between colliding

nuclei while the decoupling of first-order equations obviates the conservatio

of total energy. These shortcomings have been partially compensated

in similar

harmonic oscillator models, but the success of the compensations has not bee

tested for anharmonic oscillators. Part of this third objective is to examine

and define the limitations of the semiclassical approximation when to

applied

anharmonic oscillators. The results will contribute

to a more complete under-

standing of the associated analytic solutions that are also based on the semi-

classical approximation.

A final objective of this study is to evaluate the influence of coupled

rotational motion on the rate of vibrational energy transfer. The necessity

of including a multitude
of vibrational states with large quantum numbers to

study their interactions required a reduction elsewhere in the complexity

of

the molecular motionto keep the problem within practical bounds. The obvious

choice wasto eliminate any account of the rotational motion by limiting the

collision geometryto one-dimensional collinear encounters. This procedure is

commonly applied throughout the literature for similar reasons and is usually

based on the presumption that collinear collisions are the most effective fo

inducing vibrational excitation. However, intuitive notions suggest that the

inelasticity of three-dimensional collisions

is partitioned among vibrational

of freedom in the molecule, in varying amounts, depend-

and rotational degrees

ing on the molecular inertial properties and the initial state. Kelly and

W o l f ~ b e r ghave
~ ~ used a fully classical model to demonstrate that collinear

9
collisions are not always the most effective for converting vibrational en

For example, atom collisions with molecules possessing widely spaced rot

states can induce vibrational transitions with very little energy converte

is then a more cor-

translational motion. Vibration-rotation energy transfer

rect descriptionof the event. On the other hand, a full account of the

coupled vibration-rotation motion in a three-dimensional collision model must

include at least all of the energetically accessible rotational states in e

vibrational level. As a result, collision energies sufficient to induce vibra-

tional transitions will encompass hundreds of multiply degenerate rotational

states in most molecules. Since the occupation of each state must be treated

as a separate variable, an extremely large system of coupled differential

equations is required whose numerical solution

is intractable for all but the

simplest cases. Fortunately, some methods have recently been introduced that

average the combined action

of degenerate states and reduce the problem to an

expensive, but tractable, size. Several of these methods are evaluated and

applied here, in conjunction with a three-dimensional semiclassical collision

model. From another pointof view, the objective is to determine the conse-

quences and validity of using a collinear one-dimensional model to predict

vibrational quantum number dependence

of vibrational energy transfer rates.

The results give considerable credibility to the preceding conclusions

of this

study derived from collinear models.

1.4 Overview of the Contents and Results

In chapter2, the basic concepts and assumptions commonly applied in the

A brief historical
analysis of vibrational energy transfer are reviewed.

review of vibrationally inelastic collision models is first presented that

provides a guide to a number of more complete review papers. The concepts

10
and physical factors that control the of
rate
energy transfer are then dis-

cussed, and the several theoretical approaches from which the rates may be

estimated are evaluated as they app1.y to the objectives of this study. The

semiclassical approximation is shown to be the most suitable approach to th

objectives previously stated.

Having established the primary theoretical approach to be one in which

3 examines the
the incident particle path is computed classically, chapter

features of the interaction potentials that determine both the internal mole-

cular motion and the classical trajectory. Arguments are presented showing

that aMorse-oscillator/rigid-rotor description of the molecule

€ s adequate

for the purposes of this study and that the classical trajectory may be det

mined from just the short-range repulsive forces between colliding nuclei.

In chapter4 , a collinear, semiclassical, collision model for predicting

V-T transition probabilities from arbitrary initial states is developed and

evaluated. Comparisons are made with equivalent, exact, fully quantum mechani-

cal solutions obtained from the literature for a broad range of collision

parameters, molecular types, and initial states. While similar comparisons

harmonic
have been made before, they have been less complete and tolimited

oscillator models of the molecule initially in the ground state. This work

includes a more extensive variation of collision parameters and tests the

application of the semiclassical approximation to an anharmonic Morse oscil-

lator in several elevated initial states. In the past, there has been a

variation of opinions on the best method of compensating for the lack of

energy conservation in the semiclassical approximation. The comparisons of

this study show that the correction is nearly the same from all methods sug-

gested and no clear choice of the best method is- possible

nor is a choice

11
necessary for they are all adequate in the range of collision energies of

4 bring to light the result

interest. Finally, the comparisons in chapter

that, while the semiclassical approximation works well for a broad range

collision parameters when the molecule is treated as a harmonic oscillator,

more realistic anharmonic oscillator model imposes some definite limitations.

When the anharmonic oscillator is homonuclear and struck by a collision pa

whose mass is less than either molecular nucleus, the semiclassical approxima

tion is very successful. However, its application to heteronuclear molecules

or to homonuclear molecules struck by a heavy collision partner produces

anomalous resonances that do not appear in an equivalent harmonic oscillato

model. These anomalies are partially eliminated when additional coupling

between the oscillator and the incident particle is introduced.

With the limitations of the semiclassical approximation established for

5 describes an investigation of the factors

anharmonic oscillators, chapter

of rates for initially excited molecules.

that influence the prediction V-T

The capability of several analytic theories for reproducing rate coefficients

predicted by a more exact numerical model is also evaluated. Unfortunately,

the most widely used and simplest analytic formula also produces the poorest

estimate of quantum number dependence. But two slightly less convenient

analytic models are found to reproduce the more exact predictions for well-

of conditions. Both favorable analytic

defined and easily identifiable ranges

models are based

on a collinear semiclassical description of the collision.

The validityof the collinear collision models used in the previous

6 using a three-dimensional semiclassical

chapters is evaluated in chapter

A complete modelis first constructed that

model developed for that purpose.

of coupled vibration-rotation states

allows an arbitrary number to be included.

12
It p r o v i d e s a b a s i s f o r e v a l u a t i n g t h e a c c u r a c y o f some approximate

formulationsinwhichthe combined e f f e c t s o f t h e d e g e n e r a t e p r o j e c t i o n states

associated with each rotational quantum s t a t e are decoupled and treated col-

lectively. The a b i l i t y t o d e c o u p l e t h e d e g e n e r a t e states makes t h e o b j e c t i v e

of t h i s p a r t o f t h e s t u d y p o s s i b l e . An "effectiveHamiltonian"approximation

is found t o b e t h e most u s e f u l , a n d it is a p p l i e d t o a s t u d yo ft h ei n f l u e n c e

o fr o t a t i o n a le n e r g yt r a n s f e ro nt h e r a t e o fv i b r a t i o n a le x c i t a t i o n . The

r e s u l t s show t h a t t h e e f f e c t s o f r o t a t i o n s c a n b e s e g r e g a t e d i n t o t h r e e

classes. F o rm o l e c u l e sl i k eh y d r o g e no rt h eh y d r o g e nh a l i d e st h a th a v e a

rotationalfrequencyonly a magnitude smaller t h a n t h e f u n d a m e n t a l o s c i l l a t o r

f r e q u e n c y ,t h er o t a t i o n a lc o u p l i n g i s l a r g e andenergytransfercanproceed

viarotation-vibrationtransitionswithvery l i t t l e conversion of t r a n s l a t i o n a l

energy. The b e h a v i o ro fm o l e c u l e sw i t ht h e s ep r o p e r t i e s i s f u r t h e rs e p a r a b l e ,

dependingonthe initial angular momentum, b u t t h e u s e o f a collinearcolli-

siongeometry is physically unrealistic in anycaseandthecorresponding

a n a l y t i c r a t e formulas are consequentlyof l i t t l e value. On t h eo t h e rh a n d ,

the third and much l a r g e r c l a s s o f m o l e c u l e s , i n w h i c h a multitude of rota-

tionallevels is containedineachvibrational s t a t e , i s n o ti n f l u e n c e d by t h e

accompanying r o t a t i o n a l motioninduced i n a t h r e e - d i m e n s i o n a lc o l l i s i o n . Rate

coefficientsobtainedfrom a c o l l i n e a r c o l l i s i o n model then reproduce a l l of

thephysicalfeaturescontainedinthethree-dimensionalresults and p r e d i c t

an essentially identical dependence on v i b r a t i o n a l quantum number when com-

pared with the net vibrational transition r a t e summed over a l l f i n a l r o t a t i o n a l

states. C o r r e s p o n d i n g l y ,t h ep r e d i c t i o n sf o rs u c hm o l e c u l e s are a l s o shown t o

b ei n s e n s i t i v et ot h ei n i t i a lr o t a t i o n a l s t a t e o ft h em o l e c u l e .T h e s er e s u l t s

lend considerable credibility to the results from c o l l i n e a r c o l l i s i o n models

13
and totheanalyticsolutionsthat dependonthem. Finally, chapter 7

summarizes the new aspects of the r e s u l t s of t h i s study and presents somecon-

siderations for additional theoretical and experimentalstudy.

14
 CHAPTER 2

CONCEPTS I N VIBRATIONAL ENERGY TRANSFER

In the preceding chapter, methods for describing the macroscopic behavior

of a v i b r a t i o n a l r e l a x a t i o n p r o c e s s were discussed. The m i c r o s c o p i ca s p e c t s

of t h e p r o c e s s were c o n t a i n e d i n a thermally averaged r a t e c o e f f i c i e n t , kv,Vv,

ofundefinednature. The r e m a i n d e ro ft h i ss t u d yc o n c e n t r a t e s on t h e p h y s i c a l

f a c t o r st h a ta f f e c t G , v ~a n do nt h et h e o r e t i c a lm o d e l su s e dt oe v a l u a t e it.

Thischapterprovides a generaldiscussionoftheconceptsleading to a

t h e o r e t i c a l model. A briefhistorical review i s g i v e n f i r s t t h a t p r o v i d e s a

commentaryon some p e r t i n e n t p u b l i c a t i o n s d e s c r i b i n g t h e v a r i o u s c o n c e p t s i n

g r e a t e rd e t a i l . The l a t t e r p a r to ft h i sc h a p t e rd e f i n e st h ec o n t r o l l i n g

dynamicandmolecularparametersaffectingkv,Vtandreviewsthegeneral con-

siderations leading to a choiceforthefundamentaltheoreticalapproachtobe

appliedintheremainderofthisstudy.

2.1 H i s t o r i c a l Summary and R e v i e w L i t e r a t u r e Guide

In the 1930's and before, the anomalous absorption and dispersion of

u l t r a s o n i c waves p r o p a g a t i n g i n g a s e s were t h e p r i n c i p a l phenomena m o t i v a t i n g

t h es t u d yo fv i b r a t i o n a le n e r g yt r a n s f e r . A l l f l u i d sa b s o r bu l t r a s o n i c waves

throughshearviscositylossesand,in most cases, through heat conduction.

By t h o s e mechanisms,they a l l d i s p l a y a c o r r e s p o n d i n gd i s p e r s i o n . However,

m o l e c u l a rf l u i d s( i . e . ,t h o s ew i t h a c a p a c i t yf o ri n t e r n a l - e n e r g ys t o r a g e )

have an additional absorption and dispersion originally accounted for by

h e u r i s t i c a l l y i n t r o d u c i n g a "bulkviscosity"intotheNavier-Stokesequations

thatdescribetheprocess.Investigatorssoonrecognized,however,thatthe

a r t i f i c i a l v i s c o s i t y was a manifestation of internal-energy absorption in the

15
 molecule. A s early as 1928, Herzfeld and Rice5 explained the origin of the

additional absorption and dispersion in terms

conceptually of collisional

energy transfer between the translational and internal degrees of freedom

a

finite rate. A few years later, Oldenberg25 discussed molecular collisions

qualitatively to show the inelasticity of rotational and vibrational moti

In 1931, Zener3,26 was the first to give a detailed mathematical treatmen

vibrationally inelastic collisions. His theory was based on a quantum mechan

ical perturbation method, referred to as a "distorted wave approximation,"

applicable to low collision energies where the transition probabilities are

small. Then, in 1936, Landau and Teller4 published their historic paper in

which the properties of the rate coefficient were explored, again from a

conceptual point of view. They used partially intuitive arguments (with no

reference to the earlier work) to show that equation (1.2) described the rud

mentary dependence of kv,v-l on v and they obtained the equally important

dependence of kv,v- on temperature, given by log kv,v-l Q

Later, interest shifted away from theoretical work addressed to ultra

sonic relaxation phenomena, but increased in the study of a very similar

inelastic molecular collision problem. The accommodation coefficient, related

to the energy transfer between gas molecules and a solid surface, was studi

extensively, first by Jackson and his coworkers27 and later by Lennard-Jone

and his coworkers.28 The paper by Jackson and Mott27b became particularly

noteworthy becauseit provided a simplified mathematical derivation

of the
I1
distorted wave approximation" still referred to in modern texts.

Only a few contributions to the field of vibrational relaxation follo

until the early 1950's. For example, one-dimensional treatments by Zener and

other early investigators were extended to three-dimensional collisions.

16
After 1950, TakayanagiBg introduced the "modified wave number" approximation

designed to reduce the numerical labor in three-dimensional problems and

applied it to rotational transitions in hydrogen. Meanwhile, Schwartz,

Slawsky, and Herzfeld30 published their well-known paper in which vibrational

transitions were treated with the distorted wave approximation. Their closed-

form analytic formulas for resonant and nonresonant transition probabilities

in collinear collisison have become the most widely used means of estimatio

until recent times. Their formulation, often referred to as the SSH theory,

was later extended to three-dimensional collisions but for a nonrotating

molecule. 3

Experimental methods for measuring vibrational relaxation times were also

developing. Improved rate data were obtained from measurementsjets32~33

in

and behind shock waves34,

3 5 at other than room temperatures. The existing

perturbation theories were not always applicable to the analysis new

of these

experimental techniques, however, because the theories were limited to low-

energy collisions pertaining mostly to near-room temperatures. In 1958,

Kerner36 obtained a nonperturbative exact solution to the Schrodinger equation

for a harmonic oscillator in the presence of a time-dependent forcing functi

The only constraint on the forcing function was that it be linear in the

oscillator coordinate. Kerner's solution was subsequently applied by

Trean~r~~

in a semiclassical treatment of high-energy collinear collisions, thereby

achieving an analytically exact formula

in closed form for the transition

probabilities of a harmonic oscillator at all collision energies.

The 1960's brought on a deluge of publications concerned with vibrationa

relaxation phenomena that has persisted to this So much experimental

day.

information became available that Millikan and White38 were able to correlat

17
empirically vibrational relaxation times afor
large number of diatomic mole-

cules in terms of the fundamental oscillator frequency and the

massreduced
of

the collision pair. Their correlation was only modestly guided by theory, ho

ever. During this period, theoretical studies were stimulateda rapidly

by

growing computer technology. Considerationof exact numerical solutions to the

collision problem became

a reasonable occupation; but vibrationally inelastic

solutions were awkward until Secrest and Johnson3' developed

a numerical method

of "amplitude density functions" that allowed one-dimensional scattered wave

functions.to be obtained efficiently. Their methods have since been extended

to treat three-dimensional collisions with vibrational and rotational

inelasticity.4O

The early 1960's also marked the appearance

someofreview articles of

modern interest that describe the various theoretical approaches in detail.

One of the first was the chapter by Herzfeld4I on "Relaxation Phenomena

Gases." His discussion is based primarily on the application to ultrasonic

absorption and dispersion, but he gives

a clear account of the early theoreti-

cal approaches in which the fundamental collision parameters are described.

He later provided a more complete account in textbook form. Cottrell and

M ~ C o u b r e ytook
~ ~ a slightly more modern approach in their book by dealing

with the quantum mechanical aspects of the collision process in greater d

However, their discussion remains physically descriptive and valuable as an

Introduction to the theoretical approximations leading to analytic solutions.

T a k a ~ a n a g iprovided
~~ the first comprehensive review of the theoretical aspects

of vibrationally and rotationally inelastic collisions covering the period up

to 1963. With the rapid developments in the field following 1963,

Taka~anagi~~

18
published a second, equally comprehensive, review covering the developments to

1965.
. .
1965 preceded the time when exact quantal
The reviews published before

solutions for vibrationally inelastic collisions were obtainable with suffi-

cient ease and confidence to serve

a basis
as for testing the approximate

methods. Prior emphasis was directed toward the comparison of approximate

theories with experiment aastest of their validity.A more recent review by

Rapp andK a ~ s a l
was
~ ~ therefore addressed, in part, to an evaluation of the

earlier theories by comparing them with exact numerical solutions. With the

greatly increased detail of information about the collision dynamics in view,

both from fully quantum mechanical and fully classical numerical solutions,

Rapp and Kassal evaluate many of the assumptions contained in the approximate

collision models and provide

a useful guide to their range of applicability.

Their article also deals with some aspects

modem
of interest such as the

transfer of vibrational energy between oscillators and the effects of oscil-

lator anharmonicity. However, at the time of Rapp and Kassal's writing, .the

new class of vibrational relaxation processes had not quite impacted the

theoretical community. Their emphasis therefore centered on the dynamics of

oscillators in or near the ground state.

The beginning of this decade brought in widespread efforts to deal with

the new requirements in the analysis of vibrational energy transfer. Rich and

T r e a n ~ rpresented
~~ a comprehensive reviewof the aspects of vibrational

relaxation in gasdynamic flows. Their discussion is devoted mainly to non-

equilibrium flow processes and hence to an application of vibrational rate

theories, but they also provide

a detailed description of many aspects of

19
 vibrational energy transfer that motivated this study and their review serves

as a n i n t r o d u c t i o n t o t h e new c l a s s o f r e l a x a t i o n p r o c e s s e s .

With numerical investigations now a p r a c t i c a l and popular approach to

molecularphysics,thisdecadebeginsthe era i n w h i c h m o l e c u l a r c o l l i s i o n s

canbestudiedin much g r e a t e r d e t a i l . Many o f t h e new methods i n "numerical

physics" are d e s c r i b e d by S e ~ r e s t ~ ~a rie n

c e n t review o f t h e i r a p p l i c a t i o n t o

r o t a t i o n a l a n dv i b r a t i o n a le n e r g yt r a n s f e r . Most methods are motivatedbythe

need t or e d u c et h en u m e r i c a ll a b o ra n de x p e n s e .F o re x a m p l e ,a c t i v i t yi nt h e

useoffully classical c a l c u l a t i o n s f o r reactive a n d v i b r a t i o n a l l y i n e l a s t i c

collisionshasflourishedwiththedevelopmentof "Monte Carlo'' o r random-

s e l e c t i o n methods f o r a v e r a g i n g t h e r e s u l t s o f many t r a j e c t o r i e s a n d o r i e n t a -

t i o n s . 48 Another new concept i s thesemiquantalapproximation,developed

independently by both Miller49 andMarcus.Alsotermedthe "classical

S - m a t r i x "t h e o r y ,t h ep r i n c i p a ld i s t i n c t i o no ft h es e m i q u a n t a la p p r o a c hf r o m

e a r l i e r semiclassical methods i s t h a ti, nt h ef o r m e rd, e g r e e so f r e e d o m

are t r e a t e d c l a s s i c a l l y b u t w i t h t h e quantum-mechanical p r i n c i p l e o f s u p e r -

p o s i t i o ns u b s e q u e n t l ya p p l i e d . While t h e method a l l o w sp u r e quantum e f f e c t s

such as t u n n e l i n g , s e l e c t i o n r u l e s , a n d i n t e r f e r e n c e t o b e s t u d i e d andhas

given reasonably accurate predictions for vibrationally inelastic collisions, 51

i t s l i m i t a t i o n s a r e n o ty e tf u l l yc h a r t e d . Two reviews..ofthetheoryhave. I

recently been published by Miller. 5 2 9 5 3

A finalmilestonethathascontributedsignificantlytotheresults of

thisstudy i s t h es u c c e s so f several e f f o r t s t o a v e r a g e t h e combined contribu-

tionsofdegeneraterotational s t a t e s andthereby make t h e s t u d y o f v i b r a t i o n -

r o t a t i o ni n t e r a c t i o n sf e a s i b l e .F o r t h c o m i n gd i s c u s s i o n si nt h i ss t u d y demon-

strate t h ef u t i l i t y of a completetreatmentoftheproblem. The f i r s t

20
successful solution to the problem was presented by
54 who
Rabitz,
formulated

an "effective Hamiltonian" that nullifies the contribution of individual pro-

jection quantum states before the equations of motion are solved. Following

his work, McGuire and KouriS5 proposed

a ftjZ-conserving" approach of some simi-

A different method of
larity to the effective Hamiltonian approximation.

reducing the rotational aspects of the problem has been studied by Pack a

his 5 6 who
coworkers, treat the rotational motiona ''sudden
in approximation,"

well known in its basic form from numerous modern textbooks on quantum m

ics. The relationship of all of these methods for decoupling the internal

angular momentum of the molecule has recently been examined by

57 Secrest.

These methods and their application represent

a large part of the current

activity in studies of vibrationally and rotationally inelastic collisions.

2.2 General Considerations

Considered in the following paragraphs are some of the general concepts

and controlling parameters that form the basis

of most theoretical models for

collisions involving a diatomic molecule. The general features of several

theoretical approaches are then reviewed to guide the choice

a methodofbest

suited to the intentions of this study.

2.2.1 Modes of Energy Transfer in Diatomic Molecules

Binary collisions involving

a diatomic molecule are not yet treated in

Ab i n i t i o approaches to the
general terms entirely from first principles.

many-body problem presented by three or more nuclei and their attendant elec-

trons are still intractable on present-day computers. Fortunately, when elec-

tronic transitions are not of concern, an adequate collision model does not

21
require an explicit description of the coupled nuclear and electron mot

instead relieson the nearly instantaneous adjustment made by the electrons

the nuclear motion. The problem then reduces to one of describing only th

dynamics of the nuclear motion during

a collision but requires interaction

potentials independently obtained by some less rigorous means.

In this study, our interest is further restricted to collisions

only of a

diatomic molecule with

a heavy structureless particle such anasatom in its

i s then confined
ground electronic state. The inelasticity of the collision

to the internal rotational and vibrational energy modes of just one mole

and we avoid the complexity of dealing with the exchange of internal en

between molecules. Energy transfer still occurs to any of several internal

modes, however, as figure 2.1 illustrates.

A characteristic of most diatomic

molecules is the widely separated vibrational eigenenergies (heavy line leve

in fig. 2.1), each witha manifold of closely spaced rotational states (light

-8
I I -* V-R "
7

1 10-
-6
-5
- 4

J /
9 6-

z 3-
2-
2.1 -
Z=O

Figure 2.1.- Modes of energy transfer a in

diatomic molecule.

22
line levels in fig.2.1). Thus, a collision with sufficient energy
to excite

vibrational motion in the molecule will simultaneously excite many rotational

states as well. The arrow labeled V-R-T (vibration-rotation-translation) in

figure 2.1 typifies those kinds of transitions. The internal energy change

appearing in the molecule will be reflected as a change in the translational

energy of the colliding pair. While a complete description

of V-R-T energy

transfer is complex, certain limited paths for energy transfer are often the

dominant mechanism and they can then be treated separately. For example,

near-resonant transitions between vibration-rotation states (V-R in fig. 2.1)

may be dominant in some molecules with a suitable initial condition. In this

case, any energy traded with translation appears only as an elastic deflection

of energy required
after the encounter. In another situation, the small amount

to induce a rotational transition within the same vibrational state makes the

fig.in2.1) probable
exchange of rotational and translational energies (R-T

at collision energies where the vibrational state of the molecule may be

ignored. The molecule is treated as a rigid rotor in such circumstances. The

analyses of these limited cases involving rotation are usually simpler than

t
\
\

(a) Three-dimensional encounter.

(b) One-dimensional collinear encounter.

Figure 2.2.- Collisional motion.
23
 t h eg e n e r a l case, b u t a three-dimensionalcollisiongeometry is s t i l l required

as shown i nf i g .2 . 2 ( a ) .I nc o n t r a s t ,a ne v e ns i m p l e rb u t more r e s t r i c t e d

treatmentofthecollision i s one i n whichno rotational transition occurs.

T r a n s l a t i o n a le n e r g y i s exchanged only with vibration (V-T i n f i g . 2 . 1 ) .

Eventsofthisnaturecanoccurin a three-dimensionalencounterofarbitrary

orientationbecausetransitionsalwaystakeplacewith a p r o b a b i l i t y less t h a n

u n i t y (makingno rotationaltransitionalsoprobable),but a f r e q u e n t l yu s e d

approach that drastically reduces the complexity of the problem i s t o assume

that the most e f f i c i e n t p r o d u c e r s o f v i b r a t i o n a l t r a n s i t i o n ' s are c o l l i s i o n s

w i t ht r a j e c t o r i e sa l o n gt h ei n t r a n u c l e a r axis of a nonrotatingmolecule. The

correspondingone-dimensionalcollineargeometry is i l l u s t r a t e d i n f i g -

ure2.2(b). A s i t t u r n so u t , we s h a l l f i n d i n t h i s s t u d y t h a t t h e c o l l i n e a r

whereunsubscripted k is Boltzmann'sconstantand p i s thereduced mass of

t h ec o l l i s i o n .I f 9 d e n o t e st h e mass ofnucleus i, t h e n u
, s i n gt h en o t a -

tion in figure 2,

Methods of p e r f o r m i n gt h ei n t e g r a l si ne q u a t i o n s( 2 . 1 ) and(2.2) are

discussed in greater detail in chapters 5 and 6 where s p e c i f i c a p p l i c a t i o n s

are made. A t thispoint, o n eo n l yn e e d st or e c o g n i z et h a to b t a i n i n gt h et r a n -

c r o s ss e c t i o n ,d a / d Q ,f r o m a f u l l quantummechanicaltreatment i s t h e funda-

mentalproblem. Once e i t h e r o f t h e s e r e s u l t s i s obtained, a c a l c u l a t i o no f

thecorresponding rate c o e f f i c i e n t s i s r e l a t i v e l y s t r a i g h t f o r w a r d .

2 . 2 . 3C o n t r o l l i n gV a r i a b l e si nV i b r a t i o n a lE n e r g yT r a n s f e r

For a c o l l i s i o n t o a f f e c t t h e v i b r a t i o n a l m o t i o n o f a n o s c i l l a t o r , t h e

disturbing force created by the impacting particle must v a r y i n a time p e r i o d

line levels in fig. 2.1). Thus, a collision with sufficient energy
to excite

vibrational motion in the molecule will simultaneously excite many rotational

states as well. The arrow labeled V-R-T (vibration-rotation-translation) in

figure 2.1 typifies those kinds of transitions. The internal energy change

appearing in the molecule will be reflected as a change in the translational

of V-R-T energy
energy of the colliding pair. While a complete description

transfer is complex, certain limited paths for energy transfer are often the

dominant mechanism and they can then be treated separately. For example,

near-resonant transitions between vibration-rotation states (V-R in fig. 2.1)

may be dominant in some molecules with a suitable initial condition. In this

case, any energy traded with translation appears only as an elastic deflection

after the encounter. In another situation, the small amount of energy required

to induce a rotational transition within the same vibrational state makes the

exchange of rotational and translational energies (R-T in fig. 2.1) probable

at collision energies where the vibrational state of the molecule may be

ignored. The molecule is treated as a rigid rotor in such circumstances. The

analyses of these limited cases involving rotation are usually simpler than

t
\
\

(a) Three-dimensional encounter.

(b) One-dimensional collinear encounter.

Figure 2.2.- Collisional motion.
23
the general case, but a three-dimensional collision geometry is still require

as shown in fig. 2.2(a). In contrast, an even simpler but more restricted

treatment of the collision is one in which no rotational transition occurs.

Translational energy is exchanged only with vibration (V-T in

2.1).fig.

Events of this nature can occur in a three-dimensional encounter of arbitra

orientation because transitions always take place with a probability less

unity (making no rotational transition also probable), but a frequently used

approach that drastically reduces the complexity of the is

problem
to assume

that the most efficient producers of vibrational transition's are collisions

with trajectories along the intranuclear axis of a nonrotating molecule. The

corresponding one-dimensional collinear geometry is illustrated in fig-

ure 2.2(b). A s it turns out, we shall find in this study that the collinear

collision modelis surprisingly useful for predicting the rate of vibrational

energy transfer when many rotational states are associated with each vibra-

tional mode. Unfortunately, the incomplete nature of the collinear model

makes it awkward to obtain a rate coefficient from the detailed collision

dynamics calculated, whereas rate coefficients evolve naturally from the

results of a three-dimensional model, as the following discussion demonstrate

2.2.2 Rate Coefficients from the Collision Dynamics

The relationships between a thermally averaged rate coefficient and th

results of a microscopic collision model depend somewhat on the theoretical

description used to model the collision. For example, a semiclassical formu-

lation in which the incident particle trajectory is obtained from the cla

equations of motion deals with collisions characterized by the parameters E

E is the initial, relative, kinetic energy in a center-of-mass

and b, where

reference frame and b is the impact parameter measuring the minimum distance
24
between mass c e n t e r s o f e a c h c o l l i s i o n p a r t n e r t h a t would o c c u r i f t h e rela-

tive p a t h were n o t d e f l e c t e d . Theoutcome is a transitionprobability, P(E,))

v-tv
between each pair of internal quantum states, v and v ' , i n c l u d e d i n t h e molecu-

l a r model. A n e c e s s a r ys t e pi no b t a i n i n gt h ec o r r e s p o n d i n g rate c o e f f i c i e n t is

t o f i r s t p r o d u c et h et o t a lc r o s ss e c t i o n , o(E)
*V r
. I nt h e semiclassical frame-

work, a t o t a l c r o s s s e c t i o n may be generated by r e p e a t i n g t h e c a l c u l a t i o n f o r

a sufficientrangeofimpactparameterstoevaluatetheintegral

Likewise, a f u l l y quantum mechanical description of both the molecule and

i n c i d e n tp a r t i c l em o t i o nf o l l o w s a similar procedure. However, t h e i n c i d e n t

p a r t i c l e p a t h is not localized s o t h e c o l l i s i o n mustbe characterized instead

by E and a f i n a ls c a t t e r i n gd i r e c t i o n , R. Theoutcome is a differential

crosssection do/dSl, which may be computed f o r a l l e l e m e n t a ls o l i da n g l e sa n d

i n t e g r a t e do v e rt h es p h e r eb ya ne x p r e s s i o n similar t oe q u a t i o n( 2 . 1 ) .I n

contrasttoanythree-dimensionalmethod,equation(2.1)or its equivalent

c a n n o tb ea p p l i e di n a c o l l i n e a rc o l l i s i o n model because b or Sl are n o t

included
v a r i a b l e sT. h u so, b t a i n i n g a(E) from a c o l l i n e a dr e s c r i p t i o n
WV'

r e q u i r e s some kind of "steric f a c t o r " o n a n " e f f e c t i v e h a r d - s p h e r e c r o s s sec-

t i o n "t ob ei n t r o d u c e d .T h e s ea d d i t i o n a la r t i f a c t s are d i s c u s s e d i n g r e a t e r

d e t a i l i n c h a p t e r s 5 and 6 w h e r e c o l l i n e a r c o l l i s i o n m o d e l s are evaluated.

Once t h e c r o s s s e c t i o n is i n h a n d ,t h ed e s i r e d rate c o e f f i c i e n t f o r

v -+ v' t r a n s i t i o n s i s o b t a i n e d by a v e r a g i n gt h ee n e r g y - d e p e n d e n tt o t a lc r o s s

sections over a thermalenergydistributioncharacterized by a k i n e t i c temper-

ature T. Remembering that E i s t h e r e l a t i v e k i n e t i ce n e r g yi n a center-of-

mass f r a m e ,t h er e s u l t is8

25
 JO

whereunsubscripted k i s Boltzmann’sconstantand v i s thereduced mass of

t h ec o l l i s i o n .I f 9 d e n o t e st h e mass ofnucleus i, thenu

, s i n gt h en o t a -

tion in figure 2,

Methods o fp e r f o r m i n gt h ei n t e g r a l si ne q u a t i o n s( 2 . 1 )a n d ( 2 . 2 ) are

discussed in greater detail in chapters 5 and 6 where s p e c i f i c a p p l i c a t i o n s

are made. A t thispoint, oneonlyneeds t or e c o g n i z et h a to b t a i n i n gt h et r a n -

sition probability, P(E,t), from a semiclassical t r e a t m e n t o r t h e d i f f e r e n t i a l

VtV
crosssection, da/dR,from a f u l l quantummechanicaltreatment i s t h e funda-

mentalproblem. Once e i t h e r o f t h e s e r e s u l t s i s o b t a i n e d , a c a l c u l a t i o no f

thecorresponding rate c o e f f i c i e n t s i s r e l a t i v e l y s t r a i g h t f o r w a r d .

2.2.3 C o n t r o l l i n gV a r i a b l e si nV i b r a t i o n a l EnergyTransfer

For a c o l l i s i o n t o a f f e c t t h e v i b r a t i o n a l motionofanoscillator,the

disturbing force created by t h e i m p a c t i n g p a r t i c l e must v a r y i n a time p e r i o d

t h a t i s comparablewithor less t h a nt h en o r m a lo s c i l l a t o rp e r i o d .O t h e r w i s e ,

a slowlyapplieddisturbancesimplyallowstheoscillatortoadjustadiabati-

c a l l y ,l e a v i n g i t s f i n a lc o n d i t i o nu n a f f e c t e d by theencounter.Conversely,

animpulsivelyappliedforce w i l l severely disturb the phase of the oscillator

motionand efficiently upset the proportions of energy in vibration, rotation,

andtranslation.Theseconditionscanbeexpressed more e x p l i c i t l y bydenot-

i n g a r e p r e s e n t a t i v e time i n t e r v a l i n which t h e c o l l i d i n g p a i r i n t e r a c t as

rc and l e t t i n g uo r e p r e s e n t h ef u n d a m e n t a ol s c i l l a t o fr r e q u e n c y . We then

26
a r g u et h a te n e r g yt r a n s f e r w i l l o c c u rw i t hi n c r e a s e de f f i c i e n c y as 'cC becomes

less t h a nt h eo s c i l l a t o rp e r i o d l / v o , t h a t i s , 'ccv0 -t 0. One way t oe v a l u a t e

themagnitudeof 'cc i s by n o t i n g t h a t t h e i n t e r a c t i o n d i s t a n c e f o r c o l l i s i o n s

influenced mainly by repulsive forces can be loosely measured in terms o f a

range
parameter L, Then 'cc 2L/u,
where u is t haev e r a g e relative c o l l i -

s i o ns p e e d I. ft h e r e l a t i v e k i n e t i ce n e r g y is E and v i s thereduced

mass, t h e nt h e relative c o l l i s i o ns p e e d is J(2E/1J.) and t h ee f f i c i e n c yo f

e n e r g y t r a n s f e r w i l l i n c r e a s e as

LV0@ -t 0

We shouldthereforeexpectthequantitiesrelatedtotheefficiencyofenergy

t r a n s f e r s, u c h as P(E,t) and a(E) , t oi n c r e a s ew i t h E and t od e c r e a s e as

v+v V
"
theoscillatorfrequency,interactionrange,ornuclear masses are made

larger. Note t h a tt h ei m p a c tp a r a m e t e r ,b yc o u l da l s os e r v e a s a measureof

t h ei n t e r a c t i o nr a n g e when i t exceeds L. Collisions at increasing b will

becomemore a d i a b a t i cw i t ha n accompanyingdecrease P(E,k). in

v-tv
The p r e c e d i n g r e l a t i o n s h i p s a r e sometimesdescribed i n terms ofan

"adiabaticity parameter"

The l a r g e r 5 becomes, t h e more a d i a b a t i c i s theencounter.Valuesof 5

below u n i t y l i e i n t h e "sudden" r e g i o n .S i m i l a ri d e a s are a p p l i e dt or o t a -

t i o n a lm o t i o n as well simplybyreplacing vo w i t ht h ef u n d a m e n t a lr o t a t i o n a l

frequency,vr.Notethatin many molecules, vo >> vr so t h a t c o l l i s i o n s i n

some energy range may b e a d i a b a t i c w i t h r e g a r d t o v i b r a t i o n s w h i l e s u d d e n i n

respect to rotations.

27
 5 can be made slightly more quantitative by con-
The effects of varying

R(E),
sidering its sequel, the "resonance function," a measure of the effi-

ciency of energy transfer. If AE(<) is the average energy transferred

in a

collision characterized by5, we can define

R(S) = AE(S)/AE(S = 0) (2.6)

where AE(S = 0) is the energy transferred in the sudden limit. Although the

computation of R(C) requires a solution of the detailed equations of motion,

the outcome for atom-molecule collisions appears approximately as

NE) e
-5
x (2.7)

Hence the efficiency of energy transfer can be expected to decrease expone

tially as the encounter becomes more adiabatic. This feature will manifest

itself in the following chapters by the use of semilogarithmic plots for

quantities relatedto R(<) when plotted as functions of the variables con-

tained in E .

2.3 Theoretical Methods for Modeling Collision Dynamics

The preceding discussion made use of simple conceptual arguments to ch

acterize the collisional transfer of energy, but an estimate of the amoun

energy transferred can be obtained only from a detailed solution of the e

tions of motion. The motion is customarily described in the literature using

one of three levelsof quantization: (1) a fully classical treatment in which

quantization is imposed artificially on the internal energy of the molecul

(2) a semiclassical approximation

before (and sometimes after) the collision,

in which the path of the incident particle is obtained classically but the

molecule response is handled quantum mechanically, ( 3and

) a fully quantum-

mechanical formulation in which all members

of the system are represented in a

quantum-mechanical wave equation. (A fourth intermediate level of quantization

28
might also be given as the semiquantal method developed by and

Marcus5' in which the phase distortions of the motion are obtained classically
but subsequently treated quantum mechanically. The validity of the semi-

quantal approximation in treating vibrational energy transfer is still a to

for study, but it appears to give satisfactory results for the few examples

At the
and has several advantages worthy of consideration.
time this study was begun, however, the implications of the semiquantal

approximation were not clearly established, precluding its further considera-

tion here.) To choose the most sudtable theoretical method for meeting the

objectives of this study, we now briefly consider the general features of ea

of the three principal methods of approach.

2.3.1 Classical Collision Theories

A large number of fully classical calculations for collisions involving

the vibrational and rotational motion of a diatomic molecule have been carri

out in recent times.

24748y 63-67 Modern results have shown ,that
when the

to the minimum vibra-

oscillator zero-point energy is included (a quantum limit

tional energy), classical calculationsfor the total transferof vibrational

energy reproduce the equivalent quantal predictions quite well. This is not

too surprising if one notes that the transfer of vibrational energy does not

depend on any pure quantum effects such as tunneling or wave interference.

However, a kind of quantum effect is ignored in a classical treatment when

continuum of is transferred to the molecule without restriction to

energy

discrete quantum increments. Collision energies in a moderate thermal range

excite only a few vibrational quanta

so that the partitioning of energy into

widely separated quantized levels, excluded in a classical treatment, may have

some influence on the molecular motion. The validity of a classical

29
description that ignores these effects is not clear. For rotational motion,

quantum selection rules impose clearly identified limitations on the path

energy transfer'throughout the internal states of the molecule. The effect

of these limitations on the total energy transferred are not very sever

molecules where the rotational energy spacing is small and continuum-like

again, the criteria for treating the rotational motion classically are not

obvious. Finally, a classical description of the collision dynamics reveals

only the total energy transferred to the molecule, but it provides no rigor

description of the manner in which the energy is partitioned among quanti

internal states. Since the objectives of this study pertain specifically to

the rate of energy transfer to individual internal states, a classical col

sion model would require considerable interpretation to produce such result

Hence the use of a fully classical description

of the collision dynamics does

not appear tobe suitable for this study and no further consideration has be

given to it.

2.3.2 QuantuwMechanical Theories

Fully quantuwmechanical calculations of vibrational and rotational

energy transfer have also been abundant in recent literature.

39,40,54-56,68

A s the opposite extreme to classical treatments, they contain a complete

description of the energy deposition and provide an exact basis for compar

with more approximate methods. The difficulties associated with a full quan-

tal formulation lie mainly in the mathematical and numerical requirements

obtain a solution. The radial motion of the system is governed by a linear

second-order differential equation with at least two independent variables.

A numerical solution involves matrix manipulation and quadrature integratio

While general methods for dealing with these numerical aspects have

30
become highly developed, their incorporation ainto
complete algorithm for the

collision process is not an inviting task. Even putting that inconvenience

aside,theexperienceofhasshownthatthecomputingtimeneces-

sary to reach
a complete solution varies as &e
the of the number of coupled

molecular internal states included in the calculation. For calculations

involving both vibrational and rotational states, this cubic dependence has

been the primary factor restricting comprehensive studies of the energy trans-

fer for all but H2.

a few special molecules like To impose similar limita-

tions on this study would yield results little different from previous work.

Several approximations to the quantal formulation have been devised which

allow solutions to be obtained with less effort. The recently developed semi-

quantal ,50 is
method49 one example, but
a much older and more easily applied

approximation is the "distorted wave" approach first proposed by Zener3,26 and

later reformulated by Jackson and

M~tt.~'~
We briefly mention the distorted

wave approximation here to show that it too is not the best choice for the

purposes of this study even though it retains much of the "exactness1'

a of

full quantal solution. The approximation has been applied in the past both to

collinear collision models42 and to three-dimensional rotational 4 3models.

Generally, it is
a perturbation method that may be carried to arbitrary order,

but its greatest advantage'

is realized by retaining just the first-order term.

As with all first-order perturbation solutions, the results are accurate only

when transition probabilities and interactions between nonadjacent states are

small. This study of excited-state transitions, in which single-quantum

transitions are expected to be large and multiple-quantum transitions to be

important, would then require at least

a second-order theory for accuracy.

The distorted wave approximation is therefore not an attractive choice here

31
 2.3.3 S e m i c l a s s i c a lC o l l i s i o n Model

A semiclassical or "impact-parameter" method f o r t r e a t i n g t h e c o l l i s i o n

dynamicshas several attractive f e a t u r e s t h a t promote i t s s e l e c t i o n as t h e

p r i m a r yt h e o r e t i c a la p p r o a c hi nt h i ss t u d y .F o ro n e , it retains a l l the

quantum-mechanical aspects of e n e r g y t r a n s f e r w i t h i n t h e i n t e r n a l states of

themoleculethat are a b s e n t i n a classical t r e a t m e n t w h i l e a v o i d i n g mostof

t h em a t h e m a t i c a ld i f f i c u l t i e sa s s o c i a t e dw i t h a f u l lq u a n t a ls o l u t i o n .I nt h e

semiclassical a p p r o x i m a t i o n , t h e S c h r o d i n g e r e q u a t i o n d e s c r i b i n g t h e c o l l i s i o n

may b er e d u c e dt ot h r e e ,c o u p l e d ,t i m e - d e p e n d e n t ,f i r s t - o r d e r ,l i n e a r ,d i f f e r -

e n t i a l e q u a t i o n s - one describing the molecular wave-function dynamics and two

classical t r a j e c t o r y e q u a t i o n s f o r t h e r e l a t i v e motion of the incident par-

ticle. When t h et r a j e c t o r ya n d wave e q u a t i o n s a r e u n c o u p l e d ,t h et r a j e c t o r y

e q u a t i o n s may b e e x a c t l y i n t e g r a t e d a n a l y t i c a l l y f o r c o l l i n e a r e n c o u n t e r s and

a p p r o x i m a t e l yf o rs p h e r i c a l l ys y m m e t r i ci n t e r a c t i o n s .C l e a r l y ,t h e s er e d u c -

t i o n sr e l a xt h en u m e r i c a lr e q u i r e m e n t sc o n s i d e r a b l y .F u r t h e r m o r e ,t h er e d u c -

tiontoobtainfirst-orderdifferentialequationsaffords a second,andper-

haps more s i g n i f i c a n t , a d v a n t a g e t o t h e semiclassical f o r m u l a t i o n b e c a u s e t h e

computation t i m e t h e n v a r i e s w i t h t h e square o f t h e number of coupled channels,

making f e a s i b l e t h e c a l c u l a t i o n o f much l a r g e r sets than might be considered

w i t h a f u l l q u a n t a l method.

From a n o t h e r v i e w p o i n t , t h e a b i l i t y t o s e p a r a t e t h e m o t i o n o f e a c h c o l l i -

sion partner in a semiclassical f o r m u l a t i o n a l l o w s a n a l y t i c s o l u t i o n s t o b e

obtainedforthefinal s t a t e ofthemolecule i f some furtherapproximations

are made.The u s e f u l n e s so ft h e s e more a p p r o x i m a t ea n a l y t i cs o l u t i o n s was

d i s c u s s e di nc h a p t e r 1, b u tt h e i ra c c u r a c yr e q u i r e sv a l i d a t i o n . The v a l i d a -

t i o n i s done most convincingly by comparing the analytic predictions with

32
numerical solutionsin which the trajectories are also obtained classically.

By choosing a general semiclassical approach, such comparisons

be included
may

as part of the results of this study. However, before a classical descriptio

of the incident particle motion can be justified, several restrictive criteri

must be met. The following section delineates the pertinent criteria that

apply to vibratioaally inelastic collisions.

2.4 Basic Criteria for the Semiclassical Approximation

A detailed derivation of the semiclassical equations of motion is pre-

sented in appendix
B. In this section, we shall discuss only the general cri-

teria necessary to justify a semiclassical formulation.

The conditions for the validity

of semiclassical theory have been exam-

ined for numerous applications in the past by many authors; but recently,

Delos et a l . 6 9 9 70 reported a careful and detailed reexamination that revealed

some of the implications and restrictions of a semiclassical collision model

in much greater depth. They show that the classical trajectory equations may

a classical
be obtained in two fundamentally separate ways: one based on

wave-packet description involving the correspondence principle, and one that

makes no reference to a conventional classical picture but is based on an

extension of the usualWKB approximation. Their work was motivated by the

observation that semiclassical models work well even at collision energies t

low to justify a localized wave-packet description of the incident particle.

Indeed, they found, by comparison with the second method for obtaining the

same classical equations, that criteria based on the localized wave-packet

in the classical wave-packet

concept were overly restrictive. Specifically,

picture, the correspondence principle leads to the classical trajectory equa-

tions only if

33
 (X/L)1/2 << 1 (2 8 )

where X is the de Broglie wavelength andL is the range of the collision

interaction. On the other hand, the

WKB approach yields the classical trajec-

t o r y equations by requiring the weaker condition

X/L << 1 (2.9)

Thus, Deloset aZ. conclude that, even when a classical picture involving th

correspondence principle is not justified, the classical trajectory equations

may still produce a reasonable description of the final molecular state. They

suggest that the classical trajectory equations are implicitly more fundamen

tal to the collision dynamics than just in the correspondence limit. The co

parisons of semiclassical and quantum-mechanical collision models for harmon

oscillators by Rapp and Kassa14’ for

andanharmonic oscillators in 4
chapter

4 , typical threshold col-

support these conclusions. For example, in chapter

lision energies for a single vibrational quantum transition correspond

to

h/L % 1, which violates even equation

(2.9), and yet the semiclassical and

et aZ. warn that by the same

full quantal predictions appear identical. Delos

rule, however, a classical interpretation of the computed oscillator dynami

during intermediate times in the collision should not be given unwarranted

(2.8).
value for conditions outside equation Since all comparisons to date

of final oscillator states, no conclusions

have examined only the predictions

can be inferred about intermediate times. These warnings suggest some caution

when coupling the classical trajectory to the molecular dynamics, for example

Delos e t aZ. continue by showing that equation

( 2 . 9 ) is notthe only cri-

terion necessary to validate a semiclassical theory. They state two further

requirements that, in combination, demand that the elastic collision trajec-

tory for all channels (internal molecular states) be approximately the same.

34
These criteria are most restrictive when several potential energy surfaces

considered and when the system is allowed to cross from one surface to ano

but the applications here, where reactive collisions and electronic transi-

tions are not considered, require only

a single interaction surface. These

additional criteria then reduce to the stipulation that the difference in

diagonal matrix elements defined by the instantaneous state of the molecule

and by the interaction potential be small. Thus, if VLk is the instantaneous

k, the criteria requiring similar elastic
diagonal matrix element for state

trajectories may be expressed by

~ .. .

(2.10)

3
With simple exponential interactions of the type most commonly used (see ch.

for examples), VLk varies with k primarily as a result of vibrational

anharmonicity. When the molecule is treated aas

harmonic oscillator and the

VLk is
interaction potential is also linear in the oscillator coordinate,

identical for all k and equation (2.10) is satisfied precisely. Conversely,

we can expect the resultsa semiclassical

of treatmentof anharmonic oscil-

to compare differently with their full

lators with nonlinear interactions

quantal counterparts than found in similar comparisons using harmonic oscil-

lators. On the other hand, V' varies only weakly with k for most molecules
kk
because the vibrational anharmonicity
is generally small. Hence a semiclassi-

cal model of anharmonic oscillators can still be expected to

a large
retain

measure of accuracy provided the differences vAn - vLk remain small.

With the preceding criteria in mind, we shalla adopt

semiclassical for-

mulation throughout this study. However, since the criteria given by equa-

tions (2.9) and (2.10) are not quantitatively explicit in establishing the

35
. range of collision parameters and molecular properties that may be suitab

applied in such
a method, much more explicit statements regarding the validity

of a semiclassical collision model will be obtained from the results in c

ter 4 . Before proceeding with numerical solutions, however, the intramolecu-

lar potential determining the molecular dynamics and the collision interacti

potential determining the perturbing forces on the molecules must first be

modeled. Chapter 3 describes these potential models and the considerations

leading to them.

36
 CHAPTER 3

INTRAMOLECULAR AND COLLISION-INTERACTION POTENTIALS

A rudimentary aspect of any collision model is the description of force

of the system. In this study, three separate nuclei

acting between elements

constitute the system in principle,

and, the forces acting
on any one of them

depend on the relative positions of all three. In practice, however, a self-

consistent potential surface is rarely known, except for the simplest systems.

Instead, the potential surface

is usually constructed in a semiempirical

manner using simpler concepts.To that end,we follow the conventional tech-

nique of considering only independent pairwise interactions. The potential

surface is then separable into three additive components, each dependent on

Two of the components include the inci-

only the distance between two nuclei.

dent particle as one nucleus and are classified here as "collision-interaction

potentials." The third component is between the two bound molecular nuclei

and termed here the "intramolecular potential." Both types are modeled indi-

vidually below.

3.1 Intramolecular Potential

Since only pairwise interactions are considered, the intramolecular

potential is independent
of the disturbance to the molecule brought by a col-

lision. The potential model is therefore based

on the spectral properties
of

an undisturbed molecule.

3.1.1 Vibrational Anharmonicity

The importance of vibrational anharmonicity in the intramolecular motion

has been emphasized several times in previous chapters and its inclusion has

37
b e e ns t a t e d as a b a s i c f e a t u r e o f t h i s s t u d y . A n h a r m o n i c i t y w i l l manifest

itself in the molecular modelby the appearance of second- and higher-order

terms i n t h e e x p r e s s i o n f o r v i b r a t i o n a l e i g e n e n e r g i e s . A minimum example is

then

+ $) - + -$)
2
Ev/6 = we (v uexe (v

The f i r s t term i n e q u a t i o n ( 3 . 1 ) is t h e f a m i l i a r r e s u l t o b t a i n e d f o r a harmonic

oscillator potential of the form

I
vo(r) = 7 Fcowe(r - re12 (3.2)

where po i s t h er e d u c e d mass of t h eo s c i l l a t o r , r i s t h ei n t e r n u c l e a r

s e p a r a t i o n a, n d re i s t h ee q u i l i b r i u ms e p a r a t i o n . Numerous p o t e n t i a l func-

t i o n s w i l l produce an anharmonic term identifiable with the second term i n

e q u a t i o n( 3 . 1 ) .I nf a c t ,a n yp o t e n t i a lf u n c t i o nw i t h a higher-order depen-

denceon r - re thanequation(3.2) w i l l do.However,two h i g h l yd e s i r a b l e

a d d i t i o n a lf e a t u r e s of t h e p o t e n t i a l f u n c t i o n are (1) t h a t i t r e a l i s t i c a l l y

r e p r e s e n t a real m o l e c u l e f o r a l l separationstodissociationand (2) t h a t i t

beofananalyticallyconvenientform.Again, several p o t e n t i a lf u n c t i o n s

havebeenproposedthat f i tt h e s er e q u i r e m e n t s( s e er e f .7 1 ,c h . 5 , for

examples). One example t h a t h a s r e c e i v e d p e r h a p s t h e g r e a t e s t a t t e n t i o n s i n c e

i t s conception i s t h a t p r o p o s e d byMorse72 i n t h e form

Intheabsenceofmolecularrotation,
Vo(r) = Do e
c -2a(r-re)
- 2e
-a (r-re)

Morse obtained eigenenergies approxi-

3 (3.3)

matedby equation (3.1) plus higher-order terms t h a t are c l e a r l y n e g l i g i b l e

f o r a l l diatomicmolecules. The p o t e n t i a l c o n s t a n t s are r e l a t e d t o t h e o s c i l -

lator frequency and anharmonicity by

Do = hwe2/4wexe (3.4)

38
where Y,,(O,$) is a normalized spherical harmonic function in the polar

angles 0 and 4 , then an analytic solution to the radial wave equation

is

obtained for integer values of v given by

where z = k ' e-a (r-re)

(3.7)

N, = [ab'r(v + l)/r'(k' - v)I1l2 J

b
and L,(z) is the Laguerre polynomial73
V

m= 0

b' = k' - ZV - 1 (3.10)

The Morse potential

is not as accurate as other more recent models (e.g.,

the function proposed by Hulburt Hir~chfelder~~),

and but its analytic conven-

ience has made its appearance in the literature seemingly second in populari

only to the harmonic oscillator. Figure 3.1 illustrates

a comparison of the

Morse function for the hydrogen molecule a with

more accurate numerical

39
 Figure 3.1- I n t r a m o l e c u l a rp o t e n t i a lf u n c t i o n sf o r H2 ( t a k e nf r o mr e f . 74,
basedonref. 75).

representao
t ibotna i n e d by t h e Rydberg-Klein-Rees
analyzing
of

s p e c t r o s c o p i ci n f o r m a t i o n . Hydrogen is anexample i n whichthe Morse p o t e n t i a l

appears a t i t s worst because of the high degree of anharmonicity associated

w i t h H2. F i g u r e3 . 1s u g g e s t st h a tt h e Morse p o t e n t i a l model shouldreproduce

themolecularpropertiesaccuratelyforvibrationalenergies a t least up t o

E, 5 D0/2. However, a comprehensivecomparisonfor H2 i s d i f f i c u l t b e c a u s e

h i g h - l y i n gv i b r a t i o n a le n e r g i e si n H2 are n o t a v a i l a b l e . They a r e a v a i l a b l e

f o r CO, however,wheretheyhaverecentlybeenmeasured up t o v = 37 u s i n g

laser-spectroscopy techniques. 77 9 7 8 Figure 3.2 compares vibrational energies

ofC0;obtainedfromthe laser measurementsanddefined by terms up t o s i x t h

o r d e r ,w i t ht h es e c o n d - o r d e r Morse expression. A s expected,valuesof

E, 5 D0/2 a r e reproducedbythe Morse f u n c t i o nw i t hr e a s o n a b l ea c c u r a c y . We

s h o u l dn o t e at this point, however,thateigenenergies are n o t as s e n s i t i v e t o

variations in the intramolecular potential as are t h e wave f u n c t i o n s o r t h e i r

o v e r l a pi n t e g r a l su s e di nc o l l i s i o nt h e o r y . Thus themeasureofaccuracy

40
 I.o EXPERIMENTAL
SIX-TERM EXPANSION
.9

.8

.7

.6

-
EV
DO
.5

.4

.3

.2

.I

1 I I 1 - I I I I
0 IO 20 30 40 50 60 70 80
V

Figure 3.2.- Vibration eigenenergies ofCO (Do = 11.108 eV).

suggested by figures 3.1 and 3.2 is not entirely representative of the corre-

sponding accuracy given toa collisional model. Nevertheless, in view of the

other inaccuracies inherent in the collision model, the Morse function has

been adopted here a

assufficiently realistic intramolecular potential model.

3.1.2 Vibration-Rotation Coupling

A remaining question regarding the molecular model pertains to its rota-

tional characteristics. In a classical picture, the vibrational and rota-

A quantum-mechanical
tional motion of the molecule are clearly coupled.

description of the molecule will produce corresponding coupling terms in the

wave functions and eigenenergies associated with vibration and rotation. The

41
task is to determine.the degree of coupling that must be retained for

purposes of this study.

Pekeris79 has solved the steady-state radial wave equation for a Mors

potential with the rotational terms included. His results can be reformulated

to better show the influence

of vibration-rotation coupling in the following

way: to second order, the radial wave function obtained by Pekeris

i s similar

in form to equation (3.7). Part of the difference lies in the parameters, b'

and k t ,which depend now on the rotational quantum number

R. Denoting the

R-dependent parameters as bR and kg, they are related to the valuesb' and

by
k' given previously for a nonrotating molecule

kR = k'(1 + cR)ll2 (3.11)

bR = k
g
(
: 1); - 2v - 1 (3.12)

where

cR = AR(3/are - 1)
(3.13)
ci = AR(2 - 3/are)

and

AR = R(R + 1)2h2/(poare3D0) (3.14)

In this extended notation, the radial wave function becomes

I - A g ~ / 2(A,~)~JJ~L;JQA~Z) (3.15)
= NvR e

-a(r-re)
in which z = k e as before and = [abRT(v
Nva + 1)/ r (kg - v) ] ll2. As

equation (3.15) shows, the wave function is distorted byAR in the coordi-

nate 2.

To evaluate the effect of vibration-rotation coupling on the molecular

model, equation (3.15) must be used in place of equation (3.7) when computing
42
theappropriateoverlapintegralsappearinginthecollisiontheoryformula-

t i o n .O b v i o u s l y ,t h a tk i n do fe v a l u a t i o nc a nb e made o n l y i n r e t r o s p e c t a f t e r

t h ec o l l i s i o nt h e o r yh a sb e e nf o r m u l a t e di nd e t a i l . However, a t t h i s p o i n t ,

w e are a t l e a s t a b l e t o i n d i c a t e t h e e x t e n t of t h e c o u p l i n g bycomputing the

m a g n i t u d e so ft h ec o r r e c t i o n st ob 'a n dk 'a n dt h ed i s t o r t i o no ft h e wave

f u n c t i o ni n t r o d u c e d by AR. C h o o s i n gt h ep r o p e r t i e so f CO as anexampleand

defining R 5 40 as t h er a n g eo fi n t e r e s t , we f i n dt h a t ,f o r R = 40,

k R / k ' = 0.997,bR = 0.96k - 2~ - 1, A% = 1.05

The o v e r l a p i n t e g r a l s are s e n s i t i v e t o small changes i n t h e wave f u n c t i o n so

theeffectofthese small c o r r e c t i o n s i s n o t c l e a r ; b u t o n e c a n see t h a t t h e

influenceofrotationalcoupling i s not a majoraspectofthevibrational

motion.

The i n i t i a l c h o i c e o f a method f o r d e s c r i b i n g t h e m o l e c u l a r p r o p e r t i e s i n

this study w a s guided by a less s e n s i t i v e b u t r e a d i l y e v a l u a t e d m e a s u r e o f t h e

v i b r a t i o n - r o t a t i o nc o u p l i n g . The eigenenergy terms a s s o c i a t e dw i t hv i b r a t i o n -

r o t a t i o n c o u p l i n g were compared w i t h t h o s e r e s u l t i n g from v i b r a t i o n a l a n h a r -

mnicity. The o b j e c t i v e w a s t od e c i d ei fv i b r a t i o n - r o t a t i o nc o u p l i n gs h o u l d

beincludedtomaintain a consistentdegreeofaccuracyintheeigenenergy

expression. The e n e r g ye x p r e s s i o nc o r r e s p o n d i n gt ot h es e c o n d - o r d e rr a d i a l

solution given by equation. (3.15) w a s shown by P e k e r i s r l 9 t o b e

We c a nt h e na s kf o rw h a tv a l u e s of R is

43
A g a i n ,u s i n gs p e c t r o s c o p i cc o n s t a n t sf o r CO, t h e r o t a t i o n a l c o u p l i n g terms

equalorexceedtheanharmonic terms when E(E + 1) 2 623[v + (1/2)]. The f o l -

lowingtable l i s t s some samplevalues.

TABLE 3.1.- ROTATIONAL QUANTUM STATESWITH SECOND-ORDER CORRECTIONS

COMPARABLE TO THE ANHARMONIC CORRECTION FORCO

0 17 0.006
1 30 .009
2 39 .012
5 58 .031
10 80 .062
20 113 .124

Thus, f o r R 1 4 0 ,t h es e c o n d - o r d e rr o t a t i o n a l terms are comparableonlywith

anharmonic terms f o r t h e f i r s t few v i b r a t i o n a l s t a t e s . The t h i r d e n t r y i n

table3.1 i s a measure o f t h e a n h a r m o n i c i t y c o r r e c t i o n t h a t may be compared

w i t hu n i t y .F o rt h ef i r s t few v i b r a t i o n a l s t a t e s , i t i s much less t h a nu n i t y

and w e may t h e r e f o r e c o n c l u d e t h a t , w h i l e a completely consistent molecular

model s h o u l d c o n t a i n v i b r a t i o n - r o t a t i o n c o u p l i n g terms, t h e i r i n f l u e n c e o n t h e

moleculardynamics i s n o te x p e c t e dt ob el a r g ei na n y case. A t t h e time t h e

molecular model w a s f o r m u l a t e d f o r t h i s s t u d y , t h e small amount ofadded com-

plexityintroduced by t h e v i b r a t i o n - r o t a t i o n c o u p l i n g terms appeared to be

g r e a t e r and a Morse-oscillator/rigid-rotor d e s c r i p t i o n w a s chosen t o e n s u r e

a n a l y t i cp r o g r e s s . The e i g e n e n e r g i e s are thenexpressed by

EVR = me(. + i) - mexe (v + +) +2 E(E + l)Be (3.17)

and t h es t e a d y - s t a t er a d i a l wave f u n c t i o n i s givenbyequation(3.7).In

r e t r o s p e c t ,t h ec o u p l e de x p r e s s i o n s of Pekerisgivenbyequations(3.15)

and ( 3 . 1 6 ) w o u l d h a v e r e q u i r e d a d d i t i o n a l c o m p u t a t i o n a l e f f o r t , b u t t h e y do

n o ti n c r e a s et h ec o m p l e x i t y of t h e f o r m u l a t i o n s u b s t a n t i a l l y .

44
3.2 Collision-Interaction Potential

The outcome of any scattering event depends strongly on at least some

features of the interaction potential; yet the shape and magnitude of intera

tion potentials are poorly known for all but a relatively few simple cases.

The potentials between elastically scattered atoms are generally well estab-

lished from both theory and atomic-beam experiments, but the interactions

influencing inelastic collisions involving diatomic molecules are still an

active subject for research and computation. The topic has been discussed

extensively in relation to the transport properties of gasese0 and, more

recently, in relation to scattering events.81 To circumvent the complexity of

the subject,we develop in this section an empirical model of the interaction

forces based on the general nature of the interaction.

The nature of the interaction forces depends greatly on the modes of

energy transfer and on the internal energy states that participate in the

collision dynamics. Herewe are interested only in nonreactive interactions

between collision partners in their ground electronic states. Even ab

then,

i n i t i o calculations for three-body systems of the type considered are diffi-

cult and still incomplete for even the simplest system, H2-H (e.g., ref. 82b).

The Born-Oppenheimer separation of electronic and nuclear motion is generally

used, but the complexity associated with electronic coupling between charge

A few cases 'have

clouds of three nuclei has limited present accomplishments.

been obtained using "self-consistent field theory" where the number of elec-

82) , H2-He (refs. 83,84), H2-Li+ (ref. 85)) ,

trons is a minimum (H2-H (ref.

but similar calculations for heavier nuclei are either less rigorous (HF-HF

(ref. 86)) or not available. Experimental determinations appear to be

equally difficult. The interaction potential cannot be measured directly but

45
must be implied from some collisionally dependent observable property in w

the potential functionis only implicitly contained. The uniqueness of the

,potential thus determined is often in serious doubt and the ofaccuracy

its

details are consequently diminished. Generally, the collision-interaction

t o be the greatest source

potential, however obtained, appears of uncertainty

in the calculation of vibrational inelastic collision dynamics for most mo

cules larger H2.

than

Despite our inability to accurately define the interaction potential, we

can at least describe its qualitative features with some confidence.

To sim-

plify the description, the potential may be separated into two major compo

nents: an average spherical component that depends only on the separation

of

the molecular mass center and the incident particle and an anisotropic com

nent that accounts for variations with the molecular orientation relative
to

the direction of the incident particle location. Figure3 . 3 is a qualitative

sketch of both components.

SPHERICAL AVERAGE
EQUIPOTENTIAL

ANISOTROPIC
EQUIPOTENTIAL

v(x)
(b) Anisotropic features.

(a) Spherical features.

Figure 3.3- Characteristics of nonreactive intermolecular potentials.

46
3.2.1 Spherical Features

The spherical component may be further divided, though somewhat arbitrar

ily, into several types of forces. They are commonly referred to as (a) short-

range repulsive forces that occur principally when two nuclei are close en

for their electronic charge clouds to overlap, (b) long-range attractive

forces that result from large separations in which the charge distributions
of

each nucleus are independently distorted, and (c) intermediate forces that

simply refer to the transition region between the preceding extremes.

The short-range forces do not lend themselves easily to theoretical

sip

plification but, fortunately, the collision dynamics of vibrationally inelastic

events are not particularly sensitive to their precise shape. Usually, the

short-range forcegradient at closest approach is the single most important

feature to the collision dynamics. Generally, theoretical attempts to model

the short-range forces have led to sums of terms like

-x/L
VSR % A(x) e (3.18)

where x is the separation distance, A(x) is slowly varying in x, and L

is a constant range parameter. Commonly,

A is also taken as a constant and

effective values of A and

L are deduced from experiment by simple comparison

with predicted results.a7. The results ab-initio

of calculations have also

been reproduced surprisingly well by equation (3.18) in interactions between

two atoms, but combination rules for cases where three interacting nuclei are

present are still a topic of discussion.

Long-range attractive forces, on the other hand, are more easily approxi-

mated from well-founded physical arguments. At separations large compared to

the intranuclear separation of the molecule, the molecule appears as an inde-

pendent multipole with some polarizability. The resulting multipole

47
interaction forces are the same both in quantum-mechanical and classical

treatments witk the general result appearing as a series in

of the
terms
form

(3.19)
n

Often the dominant terms are induction forces (dipole-induced dipole) and

London dispersion forces (similar to dipole-induced dipole), which both vary

as

(3.20) v = -c/x6
The single term represented by equation (3.20) has commonly been used to

approximate the influenceof long-range forces.

Numerous empirical representations for the entire potential have emerge

from considerations similar to those just described.

An immediate choice

would appear to be the Buckingham potential

-x/L
VB=Ae - c/x= (3.21)

but this form has the unrealistic property of reaching a maximum for small

x + 0.
and becoming infinitely negative as A more realistic formula that

emphasizes the same long-range force dependence is the well-known Lennard-

Jones 12-6 potential:

(3.22)

po, explicitly appearing in equation (3.22),

The zero-potential separation,

provides a useful measure of the equivalent "hard-sphere" radius that will be

required in the collinear collision model application described in 5chapter

.

D, is also an explicit parameter.

Similarly, the well depth, The Lennard-Jones

potential gained early popularity in the analysis of transport properties in

po and D, have been evaluated for many gas

gases and its effective constants,

48
mixtures using viscosity data and virial coefficients.
8 o Unfortunately, the

mathematical form of equation (3.22) is inconvenient for the calculation

of

interaction overlap integrals in a collision model where the oscillator is

treated quantum mechanically. For that reason, we shall seek a more conven-

ient representation, but

we can use the Lennard-Jones potential as a basis for

comparison.

A potential representation consisting of exponential terms is particularly

convenient in the mathematics

of anharmonic ,oscillators. One such representa-

tion is the Morse potential

V M = D e-(x-xo)/L - ZD e- (x-xo) /2L

(3.23)
to the Lennard-
where the separation at the potential minimum, xo, is related

Jones zero-potential separation by .

x = 2lI6pO. Equations (3.22) and (3.23)

can thenbe made to yield similar potentials in the region of the potential

well by a suitable choice of L. However, the shape of the potential well is

usually not important to the collision dynamics at energies sufficient to

induce vibrational transitions. The threshold energies for vibrational tran-

sitions are near E = hue = 0.2 to 0.5 eV, while apparent well depths for

many-electron molecules likeN2, C O Y 02, etc., are typically D 2 0.01 eV.

Thus, E/D >> 1 in most cases of interest and the influence of the potential

well shape is negligible. Instead, the choice of range parameter,

L, will be

dictated by the greater necessity for properly matching the potential gradient

where V 2 E. This latter requirement for gradient matching suggests that,

unless the potential shape is correct in the region of short-range forces,

the effective range L will depend on E. Later comparisons of theoretical

and experimental rate coefficients will show that such behavior is obtained

49
 and t h e t h e r m a l r a n g e o f a p p l i c a b i l i t y f o r a given set o f p o t e n t i a l p a r a m e t e r s

is c o r r e s p o n d i n g l y l i m i t e d .

Arguments similar t o t h o s e r e g a r d i n g t h e p o t e n t i a l w e l l regionallowus

tofurthersimplifytheinteractionpotentialrepresentation(forthepurposes

of t h i s s t u d y ) by a l s on e g l e c t i n gt h el o n g - r a n g ef o r c e s . The r o l e o f t h e

long-range attractive f o r c e s i s b a s i c a l l y t w o f o l d d u r i n g a c o l l i s i o n event -

they accelerate t h ei n c o m i n gp a r t i c l e by an amount r e l a t e d t o D/E andthey

induceearlytransitionsbetween levels whoseenergyspacings are t h e o r d e r o f

D. Only r o t a t i o n a l t r a n s i t i o n s w i t h i n a g i v e nv i b r a t i o n a l s t a t e are a f f e c t e d

i n t h e latter r o l e .I nt h ef i r s tr o l e ,t h ee f f e c to fl o n g - r a n g ef o r c e s will

be apparent only a t energiesverynearthresholdandhenceonly a t very low

temperatures. However, t h i s s t u d y i s n o td i r e c t e d a t low-temperatureapplica-

t i o n si np a r t i c u l a r .I nt h e i rs e c o n dr o l e ,l o n g - r a n g ef o r c e s would be impor-

t a n t i f w e were i n t e r e s t e d i n p u r e r o t a t i o n - t r a n s l a t i o n e n e r g y t r a n s f e r o r i n

the detailed final rotational state ofthemoleculeafter a collisioninvolv-

i n g V-R-T e n e r g yt r a n s f e r . We shallfind, however, t h a t t h e n e t r a t e ofvibra-

tionalenergytransfer is notparticularlysensitivetotherotational dynam-

i c s d u r i n gt h ee a r l yo r l a t e s t a g e so ft h ee n c o u n t e r . The r o t a t i o n a l s t a t e o f

themoleculehavingthegreatestinfluence on i t s f i n a l v i b r a t i o n a l c o n d i t i o n

w i l l be the rotational s t a t e occupation occurring at the t i m e ofclosest

approach when t h es h o r t - r a n g ef o r c e s are dominant.Thus, w e c a nj u s t i f i a b l y

n e g l e c tt h el o n g - r a n g ef o r c e se n t i r e l yf o rt h e s ep u r p o s e sa n da d o p tt h es i m p l e

and a n a l y t i c a l l y c o n v e n i e n t r e p u l s i v e p o t e n t i a l

V = A e
-x/L
(3.24)

The e f f e c t s o f t h e p o t e n t i a l w e l l on v i b r a t i o n a l e n e r g y t r a n s f e r h a v e

b e e ni n v e s t i g a t e di ng r e a t e rd e t a i lb yo t h e r s . 8 8 - 9 0T h e i rf i n d i n g ss u p p o r t

50
the conclusion that the well may be neglected when E/D or >> 1.
hwe/D

There are examples, of course, where the well depth is larger (e.g., for

H,-Li+, hwe/D = 0.2). For those cases, the entire interaction potential must

be accurately represented.

3.2.2 Anisotropic Features

The anisotropic potential component is responsible for rotational distur-

bances to the molecule. Figure3.3(b) illustrates the typical magnitude

of

anisotropy effective during the collision. The magnitude is gauged by noting

re = 0.1 nm,
of most diatomic molecules is near
that the equilibrium separation

of closest
while the distance approach during a collision will be only

slightly less than the zero-potential radius,

po. For most common molecule-

atom interactions,p o = 0.3 nm. Figure 3.3(b) is drawn for the ratio

po/re = 3 with a radiuspo centered on each molecular nucleus. The equi-

potential appears mostly spherical with relatively small aspherical components.

The small anisotropic terms of most calculated interaction potentials confirm

these observations.

When rotational motion is considered, it is most conveniently described

by a coordinate system containing an angle,

6, that defines the rotation
of

the molecular axis relative of the incident particle. Fig- - . -

$0. t,he, position

ure 3.4 illustrates such a coordinate system. The subsequent mathematics then

appear in a convenient format if the potential is expressed as a series

expansion of Legendre polynomials,PJ, in the form

V(x,r,6> = pJ(cos
uJ(x,r) 6) (3.25)
J

In most cases,ab-initio potentials are represented by equation (3.25) using

only two or three terms.

51
 I I

\MOLECULE MASS CENTER

Figure 3.4- Three-dimensionalencounternomenclatureviewed i n t h e time-

dependentplanedefinedbythelocationoftheincidentparticle A and
i n t r a m o l e c u l a r a x i s BC.

The t y p i c a l l y small anisotropy of most i n t e r a c t i o n s makes two s i m p l i f y i n g

assumptionsreasonablethatgreatlyreducethecomplexityof a three-

d i m e n s i o n a lc o l l i s i o n model. One i s o p e r a t i v e i f t h e i n c i d e n t p a r t i c l e motion

-

i s t r e a t e dc l a s s i c a l l y . An a p p r o x i m a t et r a j e c t o r y may t h e nb eo b t a i n e du s i n g

o n l yt h es p h e r i c a l component o f t h e p o t e n t i a l . Suchanassumptionneglects

o u t - o f - p l a n ed e f l e c t i o n sa n dr e d u c e st h et r a n s l a t i o n a lm o t i o nt o t w o dimen-

s i o n s .A v e r a g i n gt h ei n i t i a lc o n f i g u r a t i o n is t h e ng r e a t l ys i m p l i f i e d . A

secondsimplification,inkeepingwithouroriginalnotions, is thattheaniso-

tropicpotentialcanbeapproximated by two a d d i t i v e s p h e r i c a l p o t e n t i a l s ,

eachcentered on a m o l e c u l a rn u c l e u s .I nc o n c e p t ,t h eu s eo fp a i r w i s ep o t e n -
. ., , ' , . , I : : . I : i , , , - , I I . ,

t i a l s ignoresthesecond-ordermutualinteractionbetweennuclei and i t a l s o

omits the shielding or shadowing of one nucleus by t h e o t h e r as viewedfrom

t h ep o s i t i o no ft h ei n c i d e n tp a r t i c l e . However, i f t h e a n i s o t r o p y i s small,

t h e s es e c o n d - o r d e rc o r r e c t i o n s w i l l be smaller. I na d d i t i o n ,t h ei n t e r a c t i o n

potentialdecreasesrapidlywithinternuclearseparation so t h a t f o r most

angles, 6, theincidentpaBticle w i l l b ei n t e r a c t i n gm a i n l yw i t ho n l yo n e

molecularnucleus a t a time. T h u s ,s h i e l d i n ge f f e c t ss h o u l db er e l a t i v e l y

52
unimportant. For the purposes of this study, the three-dimensional interac-

tion potentialis therefore simulated by two noninteracting short-range poten-

( 3 . 2 4 ) and each centered on a molecular nucleus.

tials, each given by equation

The final step

in representing the potential is to express it in the form giv

by equation ( 3 . 2 5 ) .

3.2.3 Three-Dimensional Interaction Potential Model

Part of the nomenclature to describe a three-dimensional encounter is

defined by figure3 . 4 . The figure lies in a time-dependent plane containing

both molecular nuclei and the instantaneous position

of the incident particle.

A n additive repulsive force between each nucleus will then produce the inter

action potential

“/L + e-+/‘) (3.26)

v(Xb,Xc> = A(e
where A and L are considered identical for both interacting pairs. The

internuclear separations may be expressed in of mass-centered variables

terms

as

where Y = [mc/(m,, + me)] is the molecular mass ratio and m, 2 %. For the

potential to appear nearly spherical,r/Z must remain small over the entire

trajectory. We have argued that it does remain less than unity since its

largest value at closest approach is only r/Z= 1/3. Equation ( 3 . 2 7 ) may

then be expanded in a uniformly convergent power series of r/Z, giving to

f ,
irst-order

53
 X b = f ( l - Y , cX
ro s 6 + . .
(3.28)
r
(l-Y),COS 6 + . ..
L X

The corresponding first-order representation

of equation (3.26) is then

(3.29)

Figure 3 . 5 demonstrates that the first-order potential, equation

( 3 . 2 9 ) , is a

(3.26),
reasonable approximation of the additive spherical potential, equation

for the typical range of parameters used here.

(3.29) is
The potential model given by equation now in a form that can b

conveniently handled in the framework of a three-dimensional collision mode

It may be transformed to a form equivalent to equation

( 3 . 2 5 ) by use of the

expansion

e
+ z cos 6 -
- 2
J= 0
(25 + l)(kl)J IJ+1/2(2) PJ(C0S 6 ) (3.30)

0
2
a
.4

0 30 60 90 120 150 180

ORIENTATION ANGLE 6, deg

Figure 3 . 5 . - Variation of a pairwise repulsive potential and its first-order

approximation with orientation angle. Calculations were done for
r/L = 5 . Solid curves are the infinite-order variation from equa-
tion ( 3 . 2 6 ) ; dashed curves are the first-order approximation,
equation ( 3 . 2 9 ) .

54
( s e er e f . 73, p. 445) where IJ+1/2 is t h em o d i f i e ds p h e r i c a l Bessel f u n c t i o n

o ft h ef i r s tk i n d and PJ i s a Legendrepolynomial as b e f o r e . By r e d u c i n g

the notation with the definition

(3.31)

e q u a t i o n (3.29) is t r a n s f o r m e d t o t h e series r e p r e s e n t a t i o n :

(3.32)

As expected, i J ( z ) d e c r e a s e sr a p i d l yw i t h J f o rt y p i c a v
l a l u e so f z so

t h a to n l y a few terms c o n t r i b u t e t o t h e summation. The correspondencebetween

e q u a t i o n s ( 3 . 2 5 ) and ( 3 . 3 2 ) i s obvious.

3.2.4 C o l l i n e a rI n t e r a c t i o nP o t e n t i a l Model

The d i s c u s s i o n s o f p r e v i o u s s e c t i o n s h a v e n o t e d t h a t a one-dimensional

c o l l i n e a r c o l l i s i o n model will b e u s e f u l i n o b t a i n i n g a n a l y t i c d e s c r i p t i o n s of

t h e rate o f v i b r a t i o n a l e n e r g y t r a n s f e r . A briefdevelopment of t h e r e q u i r e d

interaction potential expression is t h e r e f o r e i n c l u d e d h e r e .

The most e f f e c t i v e c o l l i n e a r c o l l i s i o n t o i n d u c e v i b r a t i o n a l m o t i o n will

b ea ne n c o u n t e rw i t ht h el i g h t e s tn u c l e u si nt h em o l e c u l e .C o l l i n e a r encoun-

ters are t h e r e f o r el i m i t e dt ot h o s e where 6 = 0. Equation ( 3 . 2 8 ) t h e n

, ,
.. .
r e d u c e st o

V(Z,r) = A e + e-(l-Y)r/L] (3.33)

Typically, r / L U- 5 while Y i s always less t h a nu n i t y so t h a t t h e second

t e r m i ne q u a t i o n ( 3 . 3 3 ) i s always much smaller t h a n t h e f i r s t . The i n t e r a c -

tion potential for one-dimensional collinear collisions is thereforetakento

be

55
 -‘t/L+Yr/L
V(5,r) = A e (3.34)

This form of the potential or a linearized version

it have
of been used for all

collinear vibrational energy transfer t h e o r i e ~ . ~ ~ ,It~ is

~ , applied
~~ in the

of a
following chapterto study the applicability semiclassical collision

theory to anharmonic oscillators.

56
 CHAPTER 4

A COMPARATIVE EVALUATIONOF THE SEMICLASSICAL APPROXIMATION

We have shown in chapter 2 that, while a semiclassical collision model

offers several advantages in a study of vibrational energy transfer, the cr

teria for its application are not explicit. Hence they offer marginal help i

evaluating the validity of the semiclassical approximation for a specific

set of conditions. We have also observed that the criteria, expressed by

equations (2.9) and (2.10), suggest that the validity of a semiclassical model

will be influenced by the oscillator anharmonicity. However, previous com-

parative evaluations of semiclassical theories45 have been only for harmonic

oscillators. Furthermore, the results, although favorable, have not been

of anharmonicity, the
entirely conclusive because, in addition to the absence

semiclassical formulation is typically only one of several approximations con-

tained in the comparisons, while all the corrections known to improve the

semiclassical predictions are not always included. The primary purpose of

this chapter is therefore to compare the vibrational transition probability

predictions from a semiclassical model for anharmonic oscillators

a with

comprehensive set of solutions from an equivalent, fully quantum mechanical,

collision model. The onZy difference in the two models is the treatment
of

the incident particle motion,

The physically incomplete nature

of a semiclassical treatment requires

to facilitate its correlation

some interpretation and correction, however,
with more exact collision models. Hence, in this chapter, we shall also deal

explicitly with the corrective aspects of a semiclassical treatment. For

example, a well-known weakness of semiclassical theories is the inherent lack

57
of energy conservation. Several methods of compensation have been suggested

that aim at interpreting either the classical trajectory energy20 or veloc-

ity42 in terms of corresponding values averaged over the collision. Compari-

sons described here between these semiclassical predictions and the exact

quantum-mechanical calculations show that, while such an interpretation is

necessary to correct the semiclassical predictions, the results are insensi-

tive to the choice of method in the energy range of practical interest.

Regardless of the corrections for energy conservation, the conventional

semiclassical treatment will be shown to fail badly in some cases. The

failures appear in the form of anomalous resonances that occur only in

monic oscillator models and are caused by an incomplete account of the o

lator compression and recoil during impact. Within the usual semiclassical

framework, the classical trajectory is computed, assuming that the oscillat

remains ina pure eigenstate having

a fixed average separation of its nuclei.

In reality, the oscillator is compressed by the impact and

a mixed-
enters

state condition in which the average internuclear separation oscillates wit

frequency components from each of the excited states. To include this

behavior in the semiclassical theory is not equivalent to conserving energy,

but it has the effect of introducing an oscillator "feedback"

on the classical

trajectory. The effect can change the entire nature of the results in some

cases. Extremely heteronuclear or anharmonic molecules, such as the hydrogen

halides, will be shown as members of the class strongly affected.

We also simplify the collision geometry used here by confining it to

collinear encounters. Direct comparisons with the fully quantum mechanical

results of reference68 are thus made possible. Calculations have been

presented in the of more

literature realistic three-dimensional encounters,
40

58
 in the ground state. They have
but mainly for harmonic oscillators initially

also been made in 6 for

chapter anharmonic oscillators in excited vibrational

many addi-
states. However, a three-dimensional collision geometry introduces

tional complexities, as
we shall in chapter 6 , and
demonstrate little would
be

gained by including it
in this chapter.

In the paragraphs to follow, a multistate semiclassical formulation

requiring numerical solution is assembled first that includes modifications o

the standard treatment to account for the effect of oscillatoron response

the
classical trajectory. The model is entirely equivalent to the fully quantum

6 8 , except for the classical treatment of the

mechanical model in reference

incident particle motion. The accuracy of a first-order perturbation theory

used by Mies21 for anharmonic oscillators is also evaluated.

As expected,

the first-order theory is suitable only where the transition probabilities

are small; but it must also be limited to cases where the oscillator fe

effects are negligible. Such cases will be shown

to pertain mainly to heavy

homonuclear molecules impacted by lighter collision partners.

4.1 Semiclassical Model for Collinear Collisions

A full descriptionof the semiclassical formulation for a general colli-

sion geometry is given in appendix

B. In this section, only the results

pertinent to collinear collisions are recalled in detail.

The collinear collision geometry is shown in 4.1 for a structure-

figure

less particle of mass,

m impacting a diatomic heteronuclear molecular with
a’
nuclear masses,m., and m
C
. %, extends from
The impacted oscillator nucleus,

the molecular mass center by a distance

yr, where y = mc/(m,, + mc). A

three-body center-of-mass reference frame is taken in which the relative

59
 OSCILLATOR
MASS CENTER

F i g u r e 4.1.- Collinearcollisiongeometry.

c o l l i s i o ns p e e d is ii. ( B a r r e ds y m b o l si d e n t i f yt h ei n c i d e n tp a r t i c l e vari-

ablestobeevaluatedclassicallyand l a t e r i n t e r p r e t e d as a v e r a g e v a l u e s . )

Except f o r t h e n o t a t i o n , t h i s c o n f i g u r a t i o n is identicaltothoseused by

Mies20 Y 21 and i n r e f e r e n c e s 45 and 68.

The i n t e r a c t i o n p o t e n t i a l t o b e u s e d h e r e is of t h e same f o r m g i v e n i n

r e f e r e n c e 68, namely,

-x/L
V(x) = A e

where L and A are constants. The p o t e n t i a l i n terms of mass c e n t e r and

oscillator coordinates defined in figure 4 . 1 t h e n becomes

The Hamiltonian for the three-body system i s given by

where t h e symbols w i t hs u b s c r i p t o r e f e rt oo s c i l l a t o rq u a n t i t i e s and t h e

o t h e r s y m b o l sd e n o t ei n c i d e n tp a r t i c l ev a r i a b l e s . The o s c i l l a t o rr e d u c e d

mass i s = m,,mc/(% + mc) and t h ec o l l i s i o nr e d u c e d mass i s

F! = ma(% + mc)/(ma + % + mc).

60
4.1.1 Incident Particle Motion

The applicationof Ehrenfest's theorem to the incident particle dynamics

guides the of its

formulation equation of motion with the quantum mechanically

In terms of quantum mechanically

averaged quantities properly included.

averaged variables, the equations of motion are

By separating the total wave function according to

so that
and treating the incident particle classically

and

(4.1)
the equationsof motion for the incident particle combine with equation

to give

d2Z - -A e -Z/L
5 7 - L

where the bracket notation implies

(,rrlL) =Jmm $*(r,t) e + (r, t)dr (4.2a)

For the purely repulsive exponential potential used here, the potential con-

stant, A , influences only the distance of closest approach, a quantity

of no

It may be removed by a
direct consequence to the transition probabilities.

61
transformation suggested by equating the potential energy at closest appro

for a stationary oscillator with the initial kinetic energy, that is,

A+-
E eX0/L
'
k
-
where E = (1/2)uij2 is the semiclassical relative collision energy before

interaction, Vkk is the time-independent diagonal matrix element defined by

(4.2b)

and $,(r) is the initial oscillator stationary-state eigenfunction. Note

that Ho is not the distance of closest approach for a nonstationary oscil-

= H
lator. However, if a new interaction coordinate is defined E as - E0'
the incident particle motion is unaffected and may then be by
described

(4.3a)

where

R(t) E
(eyrlL
kk'/)
(4.3b)

The variable R(t) represents the quantum-mechanical average effect of the

oscillator motion on the classical path. It is a measure of the oscillator

distortion during impact and subsequent "ringing" afterward.

To compute the trajectory classically,

we must first describe the oscil-

lator motion to obtain R(t). The usual practice at this point has been to

consider the oscillator fixed in its initial pure eigenstate

so that

$(r,t) $k(r). Then R(t) FZ 1 for all time and the classical equation of

motion is reduced to the equationfor a constant energy trajectory:

-
d2Z E -E/L
"
e ( 4 4)
V 7 P - L

62
Equation (4.4) can be integrated
analyti~ally~~
so that the interaction poten-

tial
(4.5a)
"kk
can be written explicitly in terms of time by use of the result:

e
-i (t) /L = sech2(E) (4.5b)

In such an approximation, the transformation parameter

E becomes the
0

distance of closest approach.

4.1.2 Oscillator Motion

The unsteady motion of the oscillator

is treated in the usual way by

expanding its time-dependent wave function $(r,t) in terms of stationary-

state Morse oscillator eigenfunctions $n(r) according to

where w = En/h and En is the nth state eigenenergy. Continuum states

n
are neglected. We showed in chapter 3 that, for the Morse oscillator,

wn = w e (
n + +) - wexe(. + +)2 .
The dynamical wave function $(r,t) describing the oscillator response
.. . . I .,
during a collision is the solution of the time-dependent Schradinger equation:

3,
where, from chapter

The solutions are invariant with the equilibrium separation

r and it may be
e
set equal to zero. The remaining potential parameters are equated to the

63
, ..-

familiar spectroscopic constants w and x according to equations (3.4) and

e e
(3.5).

The solution of equation (4.7) is reduced

a standard
in way (see appen-

dix B) to a set of linear, coupled differential equations for the expaFsion

coefficients defined in equation(4.6). Denoting

and incorporating the form of the interaction potential in equation (4.5a), t

(4.6) vary in time according to

the coefficients in equation

k at
The probability that an oscillator, initially in state t = -03, will

reside in state n at t = +, is
then P(E) = I cn(m) I with the initial
k-m
conditions I cj (-a) I = Cikj, where 6 is a Kronecker delta.
kj
The matrix elements given in integral form by equations (4.2b) (4.8)and
may be evaluated analytically.20,68 If, for convenience of notation, we

define a = y/aL and B = x - l , then

e
N N
n j r(B - a+j-n -r(1 + a + j - a)r(s - a - 1 - j - n + a)
V
nj
= Ba
a n! a!(j -a)!r(l + a + j - n - a ) r ( s - 2j + 2)
R=0

where k(C) is the gamma function73 with argument5, and the normalization

constants are

Nm = - 2m)1
m) li2

To stay within the maximum exponent constraints imposed by most computers,

evaluation of matrix elements with large indices requires the ratios of gamma

64
functions to be reduced to products of algebraic terms and a residual gamma

function with an argument less than 73unity.

4.1.3 Coupling of the Oscillator Motion and the Classical Trajectory

The term e in equation (4.9) may be evaluated either from equa-

tion (4.5b) or by the coupled integration of equation (4.3), depending on

the treatment of R(t). The former case ignores any coupling between the

oscillator and the classical path, thus assuming R(t) = 1 for all t. The

latter case requires evaluation of

R(t) in terms of the expansion coeffi-

cients - a task easily done by combining equations (4.2)(4.6)

and to give

(4.10)

where k again denotes the initial state.

Equation (4.10) characterizes the classical nature of the quantified

oscillator motion. The motion will become oscillatory as soon as a mixed-

state condition is produced during the collision and willso remain

afterward.

Near closest approach, large transient excursions ofR(t) occur, reflecting

the oscillator compression and recoil.

4.1.4 First-Order Perturbation Solutions

From a practical viewpoint, the convenience of an analytical solution

warrants even the coarsest assumptions, provided the limits of applicability

are understood. This study attempts to confirm those limits for a first-order

perturbation analysis applied to anharmonic oscillators in initially excited

states. We shall see that the perturbation solutions are quite successful

within their intended limits and will serve as us(efu1 approximation in many

cases.

65
 An analytical solution of equation (4.9) may b e o b t a i n e d i f t h e m o t i o n o f

t h e classical p a r t i c l e i s d e s c r i b e d by equation(4.4).Foran i n i t i a l state

k ,t h ep e r t u r b a t i o n method f u r t h e rr e q u i r e st h a t Ic k ( t ) I zz 1 and

[cn(t) 1 << 1 t h r o u g h o u tt h ed u r a t i o no ft h ec o l l i s i o n . Then o n l yt h e

i n i t i a l and f i n a l states are c o u p l e d , a l l o w i n g e q u a t i o n ( 4 . 9 ) t o b e w r i t t e n i n

t h e i n t e g r a l form:

ICn(") I = 1 E 'nk
--
'kk Jm
-03
sech2(z)exp [gJt
0
rnk(t')dt' ]1dt
2
(4.11)

with

Equation(4.11) may b e i n t e g r a t e d t o g i v e 2 1

nk
P(E) = 21~gpLii M(l
Vkk h sinh(.rrg)
+ ig,2,i2A) (4.12)
km

where
L(wn - wk) ~ L i j 'nn - 'kk
g = -U , x=- h
'kk
andM(l +ig,2,i2X) i s theconfluenthypergeometric series w i t h complexargu-

ments. The n e c e s s i t y of complex a l g e b r a may beavoided when computing t h e

modulus IM(1 + i g , 2,i2A) I by n o t i n g i t s r e l a t i o n t o t h e Coulomb wave func-

t i o nw i t hz e r oi n d e x . 73 The r e s u l t i s

IM(1 + ig92,i2h)I = Oo(-g,A) (4.13)

where

66
I

with A1 = 1 and A2 = -g.

The r e m a i n i n gc o e f f i c i e n t s are obtainedfrom

4.1.5 Numerical S o l u t i o n Methods

S o l u t i o n st ot h ec o u p l e d s e t ofequations(4.3)and(4.9) were o b t a i n e d

by f i r s t s e p a r a t i n g e q u a t i o n ( 4 . 9 ) i n t o a s e p a r a t e set f o r e a c h 'complex com-

ponentandadoptingtheequivalentof a multiple-state, close-coupling

approach.Numericalintegration w a s accomplishedwith a polynomialextrap-

olation algorithm originally developed by B u l i r s c h a n d S t o e r g l a n d g i v e n i n

-. . -
FORTRAN by Gear. 92 Fifth-order polynomials and a required accuracy of one

part in lo8 seemed t o o p t i m i z e t h e c a l c u l a t i o n of a s e l e c t e d t e s t caseand

allowed a c o m p l e t e e n c o u n t e r t o b e computed i n 50 t o 1000 steps, depending on

t h ec o l l i s i o ne n e r g y and t h e number ofcoupled states. S o l u t i o n s were s t a r t e d

with the molecule in a pure eigenstate and with the incident particle at a

d i s t a n c es u c ht h a t h ei n t e r a c t i o np o t e n t i a l had a v a l u e times t h e esti-

mated v a l u e a t c l o s e s ta p p r o a c h . The c a l c u l a t i o n w a s terminated a t anequal

d i s t a n c ea f t e rt h ee n c o u n t e r . A l l valuesof I cn(t) I were s u f f i c i e n t l y

constant a t termination. The c l o s u r er e l a t i o nx I c n ( t ) I = 1 w a s used

n
t h r o u g h o u tt h ee n c o u n t e rt om o n i t o ra c c u r a c y .I ft h ei n i t i a l state quantum

number were k, s t a t e s from n = 0 t o 2k were included a t t h e maximum ener-

gies considered to ensure that the solution w a s u n a f f e c t e d by n e g l e c t e d states.

Of c o u r s e , i n t h e e n e r g y r a n g e w h e r e t h e p e r t u r b a t i o n t h e o r y was successful,

as few as two states were adequate. Thecomputing times r e q u i r e d t o o b t a i n

a l l thematrixelementsandtointegratethedynamicsof a twelve-state model

w a s approximately 0.1 sec/step on a s i n g l e p r e c i s i o n ( 1 4 - d i g i t ) CDC-7600

computer.

67
4.2 A Comparison With Fully Quantum Mechanical Solutions

The availability of tabulated results for exact quantum mechanical ca

lations6* over a broad range of collision parameters provides an excellen

opportunity to evaluate the semiclassical approximation in this application

The extent of the examples covered is characterized by of

thethe
range
mass

parameter m = m m/ %(ma
a c
+ % + mc). For the cases chosen, m varies from

0.006 for Br2-H collisions to

3.7 for HBr-He collisions. (Reference68 labels

one data set as Br2-H2, but uses a mass parameter corresponding toA Br2-H.)

full range of oscillator frequency and anharmonicity is also represented.

Figures 4.2(a) to (f) compare the predictions of the semiclassical theory and

68 for
its first-order approximation to a sampling of the results in reference

the homonuclear oscillator cases. The semiclassical transition probabilities

are plotted as
functions of the normalized initial kinetic energy of the
-
incident particle,E/hw
e
. 68, hereafter
The probabilities from reference

referred to as "exact," are shown at energies displaced according to a tra

tory symmetrization scheme (to be discussed). In the paragraphs to follow,

the comparisons in figures 4.2(a) to (f) are used to evaluate the validity of

several methodsof compensating for the lack of energy conservation in the

semiclassical approximation and to demonstrate the influence of coupling

between the recoiling quantum-oscillator and the classical incident-particle

mot ion.

4.2.1 Energy Conservation and the Classical Parameters

The absence of energy conservation in the semiclassical approximation

E assigned
requires an interpretation of the initial relative kinetic energy

to the classical trajectory. It may be considered an effective value,

68
 I I

10'' 10- '

10-2 10-2

Pk-n Pk-n

I0-3 I0-3

10-4 I0 4

10-5

Figure 4.2.- Comparisonsof s e m i c l a s s i c a l andquantum-mechanica168 t r a n s i t i o n p r o b a b i l i t i e s of homo-

nuclearmolecules. All c a l c u l a t i o n s are done f o r L = 0.02 nm. Open symbolsdenotepointstabu-
l a t e idrne f e r e n c e 68 and plotted according to
equation(4.15). The curves are semiclas-
sical multistate solutions using classical trajectories coupled to the oscillator motion via
equation ( 4 . 3 ) . The curves -- -are t h e same withoutcoupllng via equation ( 4 . 4 ) . The curves
Ch
\D curves - - - - are first-order perturbation solutions given by equation (4.12).
 I I

10-1 10-1

10-2 10-2

Pk--n Pk-n

10-2 I0-3

I o4

10-5
0
L 2 4 6 8 1 0 1 2
E/hwe

(c) = 0) -
H c o l l i s i o n s ; coupled and uncou- ( d ) Br2(k = 0) - H c o l l i s i o n s ; coupled and uncoupled
p l e d solutions are superimposed, s o l u t i o n s a r e superimposed, 0 : k + n = 0 + 1;
o : k + n = O + l ;O : k + n = O + 3 . o : k + n = O + 2 ;O : k + n = O + 3 .

Figure 4 . 2 . - Continued.
h
IO“ IO”

10-2 10-2

10-2 10-3

Pk-n Pk-n

IO-^ IO-^

10-f I0-5

(e) N2(k = 0) - (N2) c o l l i s i o n s ; 0: k + n = 0 + 1; (f) N2(k = 2 or5) -

(Np) c o l l i s i o n s ;
0 : k + n = 0 + 2. (N2) denotes N2 treated o : k + n = 2 + 3 ; o : k + n = 2 + 4 ;
a s a s tp
rua rc t iucrleel. e s s A:k+n=5+6.

4 Figure 4 . 2 . - Concluded.
w
 a v e r a g e do v e rt h et r a j e c t o r yf r o mt h et r u ei n i t i a lv a l u e Ek tothefinal

value when,themoleculeundergoes a t r a n s i t i o n from s t a t e k t on . If

En 9
t o t a le n e r g y is conserved, ET, Ek, and En a r e r e l a t e d by

Ek + hwk = ET = E
n
+ hwn (4.14)

No f o r m a lg u i d e l i n e s a r e a v a i l a b l e , however , f o r s i m p l y r e l a t i n g E to the

e x a c te n e r g i e s Ek and En. P e r h a p st h ec l o s e s to n ec a n come i s w i t ht h e

method d e s c r i b e d i n r e f e r e n c e 4 2 , w h e r e t h e f o r m u l a t i o n o f a linearized

quantum-mechanicalapproximation i s compared t o i t s semiclassical c o u n t e r p a r t .

Expressions for the transition probabilities given by both approximations

- -u
become similar i f E is d e f i n e d by t h ea v e r a g ev e l o c i t y = (un + x)/..
Another approach i s taken by Mies, 2 1 who u s e s t h e i n t u i t i v e l y a p p e a l i n g

a r i t h m e t i ce n e r g ya v e r a g e = (En + Ek)/2. Combined withequation(4.14),

the total energy can then be related to the average energy according to

ET = E + h (wn + wk)/2 (4.15)

where h(w
n
+ wk) / 2 i s t h eo s c i l l a t o re n e r g ya v e r a g e do v e rt h et r a n s i t i o n .

Occasionally,eventhegeometricaverage E = (E E )ll2
k n
hasbeensuggested. 69

Equation(4.15) w a s c h o s e nh e r ef o rt h ec o m p a r i s o n si nf i g u r e s4 . 2 ,w h e r e it

i s shown t ob eg e n e r a l l ys u c c e s s f u l . It c o r r e l a t e st h ep r e d i c t i o n so fb o t h

t h e o r i e s for a l l i n i t i a l s t a t e s , t r a n s i t i o n s , a n d mass r a t i o s t e s t e d and

a p p e a r sa p p l i c a b l ef o r a l l energies
-E from t h r e s h o l d up t o a t l e a s t t h e

f i r s tp r o b a b i l i t y maximum. Figure4.2(c) shows c o r r e l a t i o n beyond t h e f i r s t

maximum. Notehowever, t h a t when t h e e f f e c t o ft h eo s c i l l a t o rm o t i o nc o u p l e d

to the classical trajectory is distinguishable,thecoupling must b e i n c l u d e d

topreservetheaccuracyofequation(4.15)(e.g., see f i g .4 . 2 ( a ) ) . The o t h e r

averagingmethods are no less a c c u r a t e , however.Table4.1 reveals t h a t a l l

72
the averaging methods described give essentially the same r e s u l t s and t h a t ,

within the range of these comparisons, the best choice cannot be selected.

Differences in the three methods ( o r a p p a r e n t l y a n y o t h e r method) w i l l o n l y

become d i s t i n g u i s h a b l e a t v a l u e s of ET >> hue,where,fromthermalconsidera-

t i o n s , ET i s beyond t h e r a n g e o f p r a c t i c a l i n t e r e s t . From a pragmatic view-

p o i n t ,e q u a t i o n( 4 . 1 5 ) i s a t t r a c t i v eb e c a u s e ,u n l i k et h eo t h e ra v e r a g e s , it

providesanenergytransformation, ET - E, independentof
-E a n da l l o w st h e

energies Ek o r En t ob ew r i t t e ne x p l i c i t l yi nt e r m so w
f i t hs i m p l e

a l g e b r a i c form. T h e s ef e a t u r e s are convenient f o r a d d i t i o n a lm a n i p u l a t i o n

such as thermal averaging.

TABLE 4.1.- A COMPARISON

OF SYMMETRIZATION METHODS APPLIED TO ANHARMONIC H2

Transitions -
T
k-+n Observed -
E = (EnEk)lj2
F i g s . 2 (a)- (b)
Note(a) Note(b)

0- 1 1.0 0.97 0.99 1.01

0- 2 1.3 1.41 1.46 1.50
0- 3 1.7 1.83 1.94 2.05

2- 3 2.7 2.75 2.76 2.78

2-4 3.1 3.14 3.20 3.26
2- 5 3.5 3.51 3.65 3.80

5-6 5.0 5.03 5.06 5.08

Note(a) The o b s e r v e de n e r g yd i f f e r e n c eb e t w e e nt h es e m i c l a s s i c a la n d
e x a c tr e s u l t sf o r a g i v e np r o b a b i l i t yn e a rt h r e s h o l d . The s e m i c l a s s i c a l
resultsincludeoscillatorfeedback.

Note(b) Computed f o r E/hwe = 6.

73
 4.2.2 Influence of Oscillator Response on the Classical Motion

The discussion to this point has been confined to homonuclear molecu

Figures 4.2 indicate that coupling oscillator motion and the classical traj

tory has a noticeable effect only for the most anharmonic Hp, and
molecule,

then only when struck by a relatively heavy particle, He. However, semicl

sical calculations for heteronuclear cases are much more sensitive to the

oscillator response. In the customary semiclassical formulation, the incident

particle dynamics are related only to its distance from the mass center
of the

molecule, and no regard is given for the location of the impacted nucleu

(e.g., see eq. ( 4 . 4 ) ) . In an extreme heteronuclear case where the impacted

nucleus is extended to a distance similar to the distance of closest

approach, the incident particle can spatially overlap the impacted nucleus

I without constraint. Of course, even the approach to this extreme situation

(4.4).
signals the failure of the assumptions leading to equation

The hydrogen-halides represent examples

of diatomic molecules whose

heteronuclear properties strongly influence the incident particle motion, w

the effects further augmented by the accompanying large anharrnonicity.

A s an

example, figure4 . 3 illustrates the behavior of HBr-He collisions, where

H is

the impacted nucleus. Similar results were obtained for HC1-He and are assume

to be characteristic for all hydrogen-halide-like molecules.. Both the semi-

classical numerical solutions and the analytical theory predict an anomalo

resonance at low energy when the classical trajectory is obtained from e

tion ( 4 . 4 ) . The resonance is a combined result of an improper trajectory and

the oscillator anharmonicity since similar calculations treating the molecul

as a harmonic oscillator behaved normally and in accordance with correspo

quantum-mechanical solutions.
68 Considerable care was exercised in verifying

74 .
 10-1

10-2

10-3

PO-I

I 0-4

I 0-5

2 4 6 8 IO 12
E/Tlwe

Figure 4.3.- Comparison of semiclassical and quantum-mechanical transition

probabilities for HBr(k = 0) - He collisions. The impact is between H
and He. The notation is the same as in figure 4.2; o denotes
k+n=O+l.

of the theoretical model rather than a numer-

the resonance as a real solution

of the analytical solution supports the

ical artifact. The similar behavior

conclusion that the effect is a real consequence of the model used. When

( 4 . 3 ) and (4.10), the resonance

oscillator motion is included via equations

disappears and the solution is more in accordance with the quantum-mechanical

results for single-quantum transitions. However, multiple-quantum probabil-

ities such as still display a low-energy anpmalous resonance. The inter-

-
polation of E for single-quantum transitions is also shown to be less

accurate, but equation (4.15) still performs well near threshold. The results

75
 suggest that the interference between the oscillator and the incident particle

is n o t f u l l y a c c o u n t e d f o r , b u t i f i t were, equation(4.15)wouldapply.

The.effects of the oscillator motion are n o t g e n e r a t e d s i m p l y b y l a r g e

e x c u r s i o n so f R(t) d u r i n gt h ec o l l i s i o n .F i g u r e 4.4
compares t h e time-

dependen't v a r i a t i o n o f R(t) w i t ha n dw i t h o u tt h ee f f e c t sc o u p l e dt ot h e

c o l l i s i o n dynamics f o r two extreme cases: (a) H2-H c o l l i s i o n s ,w h e r et h e

e x c u r s i o n s of R(t) are l a r g e s t ,b u tt h ee f f e c t is n e g l i g i b l e ;a n d( b ) HBr-He

c o l l i s i o n s , where t h e e x c u r s i o n s are smaller, b u t a pb.ase s h i f t i s introduced

in the oscillator motion that severely alters the remaining oscillator

response.

1.6 - E/h&=6.5g!
I
\

R
1.2 -
t1'1 \
.8 - \ l t

.4 -

0' I I I I I I I I
-6 -4 -2 0 2 4 6 8 IO
UV2L

Figure 4 . 4 . - T r a n s i e n to s c i l l a t o re f f e c t s on t h e i n t e r a c t i o n p o t e n t i a l ; R is
d e f i n e d by e q u a t i (o4n. 3 bC)u. r vdees n ottpheoe t e n t i a l term w i t h
the oscillator motion coupled to the classical trajectory; curves ----
d e n o t e t h e p o t e n t i a l term withoutcoupling.

76
4.2.3 A p p l i c a b i l i t yo fF i r s t - O r d e rP e r t u r b a t i o nT h e o r y

F i g u r e s 4 . 2 and 4 . 3 amply d e m o n s t r a t e t h e f a c t t h a t , when t h e o s c i l l a t o r

i s anharmonic,notonlymust b e small f o r t h e f i r s t - o r d e r p e r t u r b a t i o n
'k+n
theory to apply but the transient motion of the oscillator must a l s o h a v e no

significanteffect on t h e c o l l i s i o n dynamics. When t h e e f f e c t s o f t h e ' o s c i l -

l a t o r motion were n e g l i g i b l e , t h e p e r t u r b a t i o n a p p r o x i m a t i o n f a i l s when

'k-m
-+ 1. F u r t h e ri n c r e a s e si n E cause Pkm t o exceedunitybeforekeaching
a maximum - a f a m i l i a r f e a t u r e o f e q u i v a l e n t h a r m o n i c o s c i l l a t o r m o d e l s . I n

the application of a perturbationapproximationtoanharmonicoscillators, a

p r o b a b i l i t y maximummay a p p e a rf o r Pk*< 1, b u t t h e maximum i s alwaysan

a r t i f a c t ofthesemiclassicalperturbationapproximationandsignalsthe

f a i l u r e of t h et h e o r yd u et ot h en e g l e c t of R ( t )v a r i a t i o n s .T h e s ec o n c l u -

s i o n s are n o t s u r p r i s i n g , b u t t h e y f u r t h e r c o n s t r a i n t h e a n h a r m o n i c o s c i l l a t o r

perturbation theory to heavy homonuclear molecules such as N2, 0 2 , a n d t h e

h a l o g e n s .F i r s t - o r d e rp e r t u r b a t i o nc a l c u l a t i o n sf o rs l i g h t l yh e t e r o n u c l e a r

moleculessuch as CO a l s o r e q u i r e c a r e f u l a t t e n t i o n . J u s t as f o r H2, c o l l i -

s i o n s of CO w i t h l i g h t e r p a r t i c l e s ( e . g . , CO-He c o l l i s i o n s ) were u n a f f e c t e d by

t h eo s c i l l a t o rm o t i o n . However, f i g u r e 4 . 5 shows t h a tp e r t u r b a t i o nc a l c u l a -

t i o n s of c o l l i s i o n s w i t h h e a v i e r p a r t i c l e s ( e . g . , CO-Ar c o l l i s i o n s )d i s p l a y

l a r g e e r r o r s due t o t h e c o u p l e d o s c i l l a t o r m o t i o n a n d a l s o d u e t o a n i n c r e a s e d

couplingofthenonadjacentoscillator states that are notincludedinthe

p e r t u r b a t i o na p p r o x i m a t i o n . A s f i g u r e 4 . 5 shows, t h e two e f f e c t s compensate

e a c ho t h e rf o rt h ei n i t i a l s t a t e chosen.Inthe CO-Ar c a s e ,t h ep e r t u r b a t i o n -

t h e o r y e r r o r s a r e n o t accompaniedbyanomalous p r o b a b i l i t y maximums i n t h e

energy range of practical interest.

77
 UNCOUPLED OSCILLATOR-
TRAJECTORY MOTION, R = I,

10-1

FIRST-ORDER PERTURBATION
THEORY,EQ. (4.12)
PI-0
10-2

COUPLED OSCILLATOR-TRAJECTORY
MOTION, R ( t ) + l

I0-3

I 0-4 I I I 1
I I I
0 2 4 6 8 IO 12
0,.INITIAL COLLISION SPEED, km/sec

Figure 4.5.- CO(k

Semiclassical transition probabilities for = 1) - Ar colli-
sions; L = 0.02 nm.

4.3 Summary

The semiclassical approximation has been applied to vibrational transi-

tions induced in anharmonic oscillators by collinear collision with inert

atoms. Multistate numerical solutions have been compared with exact quantum-

mechanical calculationsof an equivalent collision model for a wide range of

initial molecular states and collision partners. The comparisons allow a

comprehensive assessment of the semiclassical approximation for the anharmon

oscillator model. The semiclassical predictions accurately reproduce the

quantum-mechanical transition probabilities for all initial collision energies

from the threshold to at least the first probability maximum if either the

semiclassical collision velocity or energy is interpreted as a simple aver

of the exact initial and final values. The accuracy of the correlation

between theories is not sensitive to the choice of averaging method.

78
I

The semiclassical approximation, in its usual form where the classical

trajectory is computed independently, was found to be applicable to heavy

homonuclear molecules such N2,

as 02, and the halogens on impact with lighter

partners. Lighter homonuclear molecules such as H2 showed poorer agreement

when impacted bya heavier collision partner. Heteronuclear anharmonic mole-

cules such as the hydrogen-halides displayed anomalous resonances at low

of the
energy that do not appear in their harmonic counterparts. The accuracy

semiclassical approximation for light or heteronuclear anharmonic molecules

was significantly improved by coupling the effects of the time-dependent

average motion of the recoiling oscillator to the classical trajectory.

A convenient, analytical, first-order, perturbation analysis for anhar-

monic oscillators was found to be accurate for small-transition probabilities,

but only if the effects of the oscillator motion on the classical trajectory

were unimportant. The analytical approximation is therefore not applicable

to significantly anharmonic and heteronuclear molecules and must be applied

with care for slightly heteronuclear molecules such

CO. as

79
80
 CHAPTER 5

VIBRATIONAL QUANTUM NUMBER DEPENDENCE OF

ENERGY-TRANSFER RATES

I n c h a p t e r 1, w e d i s c u s s e d t h e s p a r s e n e s s o f e x p e r i m e n t a l a n d t h e o r e t i c a l

efforts to describe the rates o f v i b r a t i o n a l e n e r g y t r a n s f e r f r o m i n i t i a l l y

e x c i t e dv i b r a t i o n a l states. The o b j e c t i v e so ft h i sc h a p t e r are t h e r e f o r e

t o examine t h e f a c t o r s i n f l u e n c i n g t h e p r e d i c t i o n ofsuch rates and t o

evaluate the validity of several a n a l y t i c f o r m u l a s i n p o p u l a r u s e f o r

e s t i m a t i n gt h e i r quantum number dependence. However, t h ea p p r o a c ht ob e

taken mustbe l i m i t e d by pragmaticconsiderations.Forexample,accurate

V-T rate-coefficient calculations by any t h e o r e t i c a l model are clouded by

uncertainties in the shape andmagnitudeof the interaction forces between

c o l l i d i n g pairs f o r a l l b u t a few s i m p l e cases. Thus, w e canexamineonly

the qualitative features that a r e n o t masked by i n t e r a c t i o n p o t e n t i a l

u n c e r t a i n t i e s .F u r t h e r m o r e ,e v e na ne x t e n d e dc o l l i s i o n modelmust retain

some a p p r o x i m a t i o n s , p a r t i c u l a r l y r e g a r d i n g t h e c o l l i s i o n g e o m e t r y , i f it

is t o remaincomputationally practical inthepredictionofthermally

averaged r a t e c o e f f i c i e n t s . Hence, a t t e n t i o n i s c o n f i n e dh e r et ot h ec o l -

l i n e a r semiclassical t r e a t m e n t d e s c r i b e d i n c h a p t e r 4 thataccuratelyrepro-
duces a l l t h e main c h a r a c t e r i s t i c s of v i b r a t i o n a l e n e r g y t r a n s f e r t o i n i -

tially excited oscillators, but offers the advantage of being further reduc-

i b l et oy i e l dc l o s e d - f o r ma n a l y t i cs o l u t i o n s . The a n a l y t i c s o l u t i o n s are of

particular interest because of t h e i r p r a c t i c a l i m p o r t a n c e i n t h e n u m e r i c a l l y

cumbersome analysis of macroscopic nonequilibrium processes for which rate

information for several modes of energy transfer must be economically

81
 provided. 1-1 The complete semiclassical model, requiring numerical solu-

tion, i s applied both to an examination of the qualitative nature of upper-

state transitions and aasbasis for evaluating the accuracy of the analyt-

ical solutions.

In the sections to follow, the features

of the collision model that

appear most important to the dynamicsa vibrationally

of excited oscillator

are first discussed, followed a by

description of several approximations,

each of which retains one or more of the features considered. Approximate

values of the interaction potential parameters and their range of uncertai

are then estimated by comparing the predicted ground-state rate coefficient

with a comprehensive set of experimental values. Collisions of CO with He

are chosen as the example because of the abundant data available. The

implied potential parameters are then used to compare the numerical model

with some experimental excited-state rate coefficients and with the analyt

predictions. Finally, the effects of multiple-quantum transitions from

excited states on
a vibrational relaxation process are considered both for

molecules like CO, where the effect is secondary, and for molecules like

the halogens, where the effect can be dominant.

5.1 Collision Model

5.1.1 Features Influencing the Excited-State Collision Dynamics

As the quantum number of the initial oscillator state is increased,

several aspects influencing the oscillator dynamics and its interactions

with the incident particle become increasingly important. For example,

the wave functions that describe vibrationally excited eigenstates become

more extended in the oscillator coordinate. Consequently, when

the

82
o s c i l l a t o r is d i s t o r t e d by a c o l l i s i o n , t h e w a v e - f u n c t i o n o v e r l a p is g r e a t e r

notonlywithadjacenteigenstatesbutwith more remote states as w e l l . This

f e a t u r e is r e f l e c t e d by t h e i n c r e a s e d m a g n i t u d e o f t h e m a t r i x e l e m e n t s

d y n a m i c a l l yc o u p l i n gt h ee i g e n s t a t e sw h i c h ,i nt u r n ,a c c o u n t sf o rt h eg r e a t e r

p r o b a b i l i t y of V-T energy transfer through both single- and multiple-quantum

t r a n s i t i o n s .F u r t h e r m o r e ,t h ei n c r e a s e dc o u p l i n g of nonadjacent states

during the collision can affect the final occupation of states a d j a c e n t t o

t h e i n i t i a l state and thereby influence the rate of single-quantum transi-

tions. Thus, a c a l c u l a t i o no ft h eo s c i l l a t o rd y n a m i c sf r o ma ne x c i t e d

i n i t i a l state must include multiple-state interactions at collision energies

wherethey are n o r m a l l y u n i m p o r t a n t f o r o s c i l l a t o r s i n t h e g r o u n d state.

The degree with which multiple-quantum transitions influence the

o s c i l l a t o r dynamicsduring a c o l l i s i o n depend, i n p a r t , on the form of the

i n t e r a c t i o np o t e n t i a l . A common p r a c t i c e ,o f t e nu s e dt os i m p l i f yt h e

analysisofground-stateoscillators, is toconsidertheoscillatormotion

small compared t o t h e r a n g e of i n t e r a c t i o n and l i n e a r i z e t h e i n t e r a c t i o n

p o t e n t i a li nt h eo s c i l l a t o rc o o r d i n a t e .I n a harmonic o s c i l l a t o r , t h i s

treatmenthastheeffectofequalizing a l l the diagonal matrix elements and

f o r b i d d i n gm u l t i p l e - q u a n t u mt r a n s i t i o n s . The occupationofnonadjacent

o s c i l l a t o r states i s ' t h e n p o s s i b l e o n l y t h r o u g h a sequenceofsingle-quantum

s t e p sd u r i n gt h ec o l l i s i o n .N o n l i n e a ri n t e r a c t i o n terms remove t h e s e

r e s t r i c t i o n s a n dm o d i f yf i n a l - s t a t eo c c u p a t i o n si n two r e l a t e d ways. First,

a l l the nonadjacent states are d i r e c t l y c o u p l e d , t h e r e b y i n c r e a s i n g t h e i r

a c c e s s i b i l i t y .S e c o n d ,t h ed i a g o n a lm a t r i xe l e m e n t s a r e no l o n g e re q u a l ,

leading to additional phase distortions in the quantum-mechanical o s c i l l a t o r

motionwhichmodify theprobabilityoftransition. The a d d i t i o n a l p h a s e

83
 s h i f t s depend on t h e p r o d u c t o f t h e d i f f e r e n c e b e t w e e n d i a g o n a 1 . m a t r i . x

e l e m e n t sa n dt h es t r e n g t ho ft h ei n t e r a c t i o n . They a p p e a r e x p l i c i t l y in a

semiclassical impact parameter treatment described by Bates93 and a p p l i e d t o

anharmonic o s c i l l a t o r s b y Mies.21 The formulationhasbeenreviewed in

s e c t i o n B . 3 ofAppendix B.

A l l the foregoing effects are a m p l i f i e d when o s c i l l a t o r a n h a r m o n i c i t y

i s included.Nonadjacent s t a t e s become c o u p l e de v e nf o rl i n e a r i z e di n t e r -

a c t i o n s and t h e l a r g e r d i f f e r e n c e between t h e d i a g o n a l m a t r i x e l e m e n t s

creates p h a s e d i s t o r t i o n s t h a t c a n become a s i g n i f i c a n t f r a c t i o n o f t h e

u n p e r t u r b e do s c i l l a t o rp e r i o d .M i e s 2 0 r 2 1h a s shown t h ei n f l u e n c eo nt r a n s i -

tion probability predictions to be large even for oscillators initially in

t h e ground s t a t e . A second,and i n some cases g r e a t e r , e f f e c t o f anharmon-

i c i t y i s i t s i n f l u e n c e on t h e v a r i a t i o n o f e i g e n e n e r g i e s w i t h quantum number.

Since transition probabilities and the related rate c o e f f i c i e n t s are known

t o depend on t h e amount o f e n e r g y t r a n s f e r r e d , a lowest-ordereffectof

o s c i l l a t o r a n h a r m o n i c i t y may be demonstrated by simply inserting anharmonic

oscillator eigenenergies into a harmonic o s c i l l a t o r t h e o r y s u c h as t h a t g i v e n

by Schwartz e t aZ. 30 The results d e v i a t e s u b s t a n t i a l l y f r o m t h e s i m p l e

Landau-Tellerrelationforthe rate coefficients given by equation(1.2)and

where k (T) d e n o t e st h e rate c o e f f i c i e n t f o r t r a n s i t i o n s f r o m state

m,m-l
m t o m-1 and i s a f u n c t i o no ft h ek i n e t i ct e m p e r a t u r e T. However, t h e

s i m p l e ad hoc i n s e r t i o n o f a n h a r m o n i c e i g e n e n e r g i e s i n t o a harmonic oscilla-

t o r model i s notalways a s u f f i c i e n t means of accounting for anharmonicity.

84
The influence of anharmonicity on the interaction matrix elements, which in

turn effects both the magnitude and phase of the oscillator motion, is ofte

so great that an anharmonic oscillator model must be used from the start.

Fortunately, osclllator anharmonicity and nonlinear interaction potentials

present onlya slight increasein computational difficulty, particularly if

a Morse oscillator and an exponential form of the interaction are adopted.

The necessary matrix elements are then conveniently expressed in closed

algebraic form just as for harmonic oscillators.

Finally, an oscillator potential creating anharmonicity also admits to

the existence of continuum states. We shall neglect their contribution to

the energy transfer process, however, since they are energetically inacces-
sible bya large margin for the combinations
of collision energies and

initial states considered here. Although their effects have not been evalu-

ated, the occupation of continuum states is presumed to be as small as the

nearby bound states, and no bound states near the continuum were found to

influence the dynamics of any states at the quantum levels of interest.

5.1.2 Aspects of the Semiclassical Numerical

Model

To obtain V-T rate coefficients, we calculate the associated transition

probabilities using the semiclassical collision model described in 4,

chapter

wherein the trajectory is constrained to collinear encounters.of One

the

penalties of using a semiclassical approximation was shown to be that total

as in chapter4 , the effects of that

energy is not conserved; but shown

omission are easily and accurately compensated for by interpreting the

relative collision energy an

asaverage of the known initial and final

values. A far more severe limitation of the semiclassical was

theory

85
 found t o b e i t s i n c o m p l e t e t r e a t m e n t o f t h e i n t e r a c t i o n when t h e o s c i l l a t o r

is veryheteronuclear-(e.g.,,hydrogen-halides). Such cases are avoided

here and have presented numerical difficulty in exact t r e a t m e n t s . 6 8

The i m p l i c a t i o n s i n t r o d u c e d by a r e s t r i c t i o n t o c o l l i n e a r e n c o u n t e r s are

n o t as w e l l u n d e r s t o o d , b u t t h e r e s t r i c t i o n is necessary if the quantum-

number dependence of thermally averaged rate c o e f f i c i e n t s is ever t o be

o b t a i n e d i n a reasonablecomputing time. C l e a r l y , a more r e a l i s t i c approach

would i n c l u d e a three-dimensional collision geometry in which simultaneous

rotational transitions are c o u p l e d w i t h t h e v i b r a t i o n a l m o t i o n , b u t t h e l a r g e

number of r o t a t i o n a l states t h a t become a c c e s s i b l e a t c o l l i s i o n e n e r g i e s

sufficient to cause vibrational transitions would make o u r o b j e c t i v e of

studying thermally averaged rate c o e f f i c i e n t s i m p r a c t i c a l f o r a l l b u t a few

s p e c i a lm o l e c u l e s ,l i k e H2. On t h eo t h e rh a n d , so long as t h e r o t a t i o n a l

eigenenergies of the undisturbed molecule are w e l l d e s c r i b e d by a r i g i d - r o t o r

model ( s u g g e s t i n g t h a t t h e r o t a t i o n a l and v i b r a t i o n a l m o t i o n s a r e s e p a r -

a b l e ) , and t h e m o l e c u l a r p r o p e r t i e s are s u c h t h a t v i b r a t i o n a l e n e r g y is

traded mainly with translation, the disparity between a collinear and a

three-dimensionaltheory is n o t e x p e c t e d t o b e v e r y s e n s i t i v e t o t h e i n i t i a l

v i b r a t i o n a l quantumnumber. Chapter 6 p r o v i d e sg r e a t e ri n s i g h ti n t ot h e

n e c e s s a r yc o n d i t i o n s .F o ro u rp u r p o s e s ,t h ec o l l i n e a rp r e d i c t i o n s are

n o r m a l i z e da c c o r d i n gt ot h er a t i o k /dl t h uasv o i d i ntghper e d i c -

msm-1
t i o n of a b s o l u t e rate c o e f f i c i e n t s a n d , h o p e f u l l y , much of t h e a b s o l u t e

e r r o ra s s o c i a t e dw i t ht h ec o l l i n e a rr e s t r i c t i o n . Such a r a t i o a l s o a b s o r b s

thelowest-order quantum-number dependencesuggestedbyequation(5.1).

86
5.1.3ThermallyAveraged Rate C o e f f i c i e n t s from a C o l l i n e a r S e m i c l a s s i c a l

Model

With t h e p o s s i b l e e x c e p t i o n o f m o l e c u l a r beam a n a l y s e s , t h e a p p l i c a t i o n s

of an inelastic collision model u s u a l l y r e q u i r e r e s u l t s i n t h e f o r m o f a

thermallyaveraged rate c o e f f i c i e n t . A g e n e r a lf o r m u l a t i o n of t h ea v e r a g i n g

i n t e g r a l is w e l l known, b u t h e r e t h e r e s t r i c t i o n t o c o l l i n e a r t r a j e c t o r i e s

and t h e u s e o f a semiclassical approximation require some s p e c i a l c o n s i d e r a -

t i o n .G e n e r a l l y ,t h e r a t e c o e f f i c i e n tf o r a k i n e t i ct e m p e r a t u r e T may be

w r i t t e n i n terms oftheenergyparameter ern = Em/kTandanenergy-dependent

c r o s ss e c t i o n u(&), w h e r end e n o t e st h ef i n a l quantum s t a t e and Em
mtn
is the relative kinetic energy before a collision with an undisturbed

o s c i l l a t o ri n a p u r ee i g e n s t a t e m. The r a t e c o e f f i c i e n t i s then similar t o

e q u a t i o n ( 2 . 2 ) , t h a t is,
ce

where
the
average
thermal
speed is
-C 0= (8kT/.rrp) and p i s the
reduced

c o l l i s i o n mass d e f i n e d by e q u a t i o n ( 2 . 3 ) . A f u r t h e rr e q u i r e m e n tf o rt h e

c o l l i s i o n model i s t h a t i t conform t o t h e d e t a i l e d b a l a n c e r e l a t i o n s .

Originatingwiththereciprocitytheorem,therequirementsofdetailed

balance propagate through three levels o f m i c r o s c o p i c d e t a i l , g i v i n g t h e

general physical relations for spinless nondegenerate collision partners as

(5.3a)

(5.3b)

(5.34

87
 where is t h et r a n s i t i o np r o b a b i l i t yf r o m state m t o nand hw is
p- m
t h eo s c i l l a t o re n e r g yo f s t a t e m.

The c o l l i n e a r c o l l i s i o n geometryproduces semiclassical t r a n s i t i o n

probabilities that behave according to equation (5.3a), b u t t h e r e s t r i c t i o n

t o a zeroimpactparameter leaves t h e c r o s s s e c t i o n r e q u i r e d by equation(5.2)

undefined. One
common s o l u t i o n i s t oa d o p ta ne f f e c t i v eh a r d - s p h e r ec r o s s

section u andcompute t h ei n e l a s t i cc r o s ss e c t i o na c c o r d i n gt o
0

(5.4a)

and

U(En) = 0 'P(q) (5.4b)

n-m O n-m
E q u a t i o n( 5 . 3 b )r e q u i r e st h a t

U'
0
= [l + R(u n - u~)/E~]u,

thussuggestingthatthe"hard-sphere"sizemustdependonthecollision

e n e r g ya n dt r a n s i t i o ni nq u e s t i o n !T h i sc o n t r a d i c t i o nr e s u l t sf r o mt h e

collinear approximation, but the error is n e g l i g i b l e when Ih (w, - urn) l/En << 1.

When t h e r a t i o a p p r o a c h e s u n i t y , t h e t r a n s i t i o n p r o b a b i l i t y i s t y p i c a l l y so

small t h a t t h e i n t e g r a l i n e q u a t i o n (5.2) i s u n a f f e c t e d .

Equation (5.2) must be modified further to compensate for the lack~.of . .

e n e r g yc o n s e r v a t i o ni n h e r e n ti nt h es e m i c l a s s i c a la p p r o x i m a t i o n . This

discrepancy is e a s i l y and a c c u r a t e l y c o r r e c t e d by i n t e r p r e t i n g t h e semi-

classical r e l a t i v ec o l l i s i o ne n e r g y
-E o rs p e e d ii as anaverageofthe

i n i t i a l and f i n a lv a l u e s . The r e s u l t s i n c h a p t e r 4 d e m o n s t r a t et h a t ,w h i l e

thecorrectioncanbelarge,the methodof averaginghas no a p p a r e n t e f f e c t

ontheoutcomeforvibrationallyinelasticcollisions a t al?energies from

88
t h r e s h o l d up t o t h e l i m i t s of p r a c t i c a l i n t e r e s t . F o r c o n v e n i e n c e , w e use

an a r i t h m e t i ce n e r g ya v e r a g e .D e n o t i n gt h et o t a le n e r g y as ET, t h e

semiclassical approximation is brought into close agreement with an equiva-

l e n t quantum-mechanical c a l c u l a t i o n by t h e i n t e r p r e t a t i o n

Combining e q u a t i o n s ( 5 . 2 ) , ( 5 . 4 ) , and(5.5)thengivesthethermalaveraging

p r e s c r i p t i o n f o r a c o l l i n e a r semiclassical c o l l i s i o n model:

where E
-
= E/kT and wm = w - w . To make t h es a t i s f a c t i o no f equa-
m n
t i o n ( 5 . 3 ~ ) by (5.6) more o b v i o u s ,t h el o w e ri n t e g r a t i o n l i m i t i n equa-

t i o n (5.6)hasbeen set tozeroeventhoughtheindependentvariabletrans-

formation
from E to E viaequation(5.5)produces a limit of
m
k Ihwm/2kTI, dependingonthesignof w The n e g a t i v e limit may c l e a r l y
mn
'

be reset t o z e r o , b u t e v e n when t h e limit i s p o s i t i v e , t h e p r o b a b i l i t y

t h r e s h o l d i s n e a r l y twice t h e limit, so t h a t a g a i n s e t t i n g it tozerohas no

effect on the integral.

5.2 AnalyticApproximations

Of t h e many a n a l y t i c a p p r o a c h e s a p p e a r i n g i n t h e l i t e r a t u r e ( s e e r e f . 45

for a p a r t i a l summary), t h r e e t h a t s t a n d o u t i n t h e i r a p p l i c a t i o n f o r

e s t i m a t i n g t h e V-T rate c o e f f i c i e n t v a r i a t i o n s w i t h quantumnumber are

(a) t h e s e m i e m p i r i c a l f o r m u l a s f o r Morse o s c i l l a t o r s o f Keck and Carrier,g4

(b)theperturbationtreatmentof Morse o s c i l l a t o r s d e v e l o p e d by Mies,21 and

(c) t h e e x a c t s o l + i o n t o a linearly forced harmonic oscillator obtained by

>..

Kerner.36 Each a p p r o a c h r e t a i n s o n e o r more o f t h e a s p e c t s o f s p e c i a l

89
 i n t e r e s tt ot h i sa p p l i c a t i o n . They s h a r e t h e common f e a t u r e t h a t all

incorporate collinear collision geometry and a l l are based on an exponentially

repulsive interaction potential (later referred to as p o t e n t i a l I) of t h e form

-X/L
V,(x) = A e (5.7)

where the coordinates are defined in figure 4.1.

5.2.1Keck-CarrierFormulaforAnharmonicOscillators

The formula obtained byKeck and Carrierg4 i s an a d a p t a t i o n o f t h e

distorted-wave harmonic oscillator theory of Schwartz e t aZ. 30 f o r a Morse

oscillator. It i n c l u d e s a n e m p i r i c a l f i t t o t h e n u m e r i c a l s o l u t i o n o f an

integral equation for the "adiabaticity factor" and provides a particularly

simple formula for estimating single-quantum transition rates from an

a r b i t r a r y i n i t i a l state. Keck and Carrier made no claim f o r t h e s u i t a b i l i t y

of their formula in applications beyond a d e m o n s t r a t i o n o f t h e r o l e o f

vibrational nonequilibrium in a d i s s o c i a t i n g gas; buttheformula was subse-

quently applied by Brayg5 i n a p i o n e e r i n g a n d d e t a i l e d c a l c u l a t i o n o f a

vibrational relaxation process for anharmonic oscillators, apparently because

of i t s s i m p l i c i t y and f o r l a c k of a b e t t e r estimate. For similar r e a s o n s ,

theKeck-Carrierformulahassincegainedwidespreaduseinthedetailed

analysisofupper-statekineticsin lasers. 11-15 Its c o n s i d e r a t i o n h e r e is

motivatedprimarily by t h e number of k i n e t i c models t h a t i n c o r p o r a t e it. The

Keck-Carrier formula can be written in a form similar t o e q u a t i o n (5.1) a s g 5

k
m,m- 1

90

.- " "_ ...

where F is obtainedfromtheempiricalformula
m

i n which

11 = "w
m,m-l
L(u/2kT) 'I2 (5.10)

The t r a n s i t i o n frequency w = w "w i s computed f o r a Morse

m,m-1 m m-1
o s c i l l a t o r as done previously by the expression

wm = w e (m + -$)- wexe (m + $) 2
(5.11)

5.2.2 Mies P e r t u r b a t i o nS o l u t i o n f o r Anharmonic O s c i l l a t o r s

The c l o s e s t a p p r o x i m a t i o n t o t h e n u m e r i c a l model used here is a

semiclassical firs t-order perturbation treatment developed by Mies. 21 It

properlyincludestheeffectsofanharmonicitybut, by t h e n a t u r e o f f i r s t -

ordermethods, i t neglectstheinfluenceof states other than the designated

i n i t i a l and f i n a l states. F u r t h e r m o r e ,t oo b t a i na na n a l y t i c a ls o l u t i o n ,t h e

classical path must be computed independently from the motion of the oscilla-

tor. The t h e o r y i s t h e r e f o r ea p p l i c a b l eo n l yt os i n g l e - q u a n t u mt r a n s i t i o n s

i n w h i c ht h et r a n s i t i o np r o b a b i l i t i e s a r e small compared t o u n i t y . As

demonstrated i n c h a p t e r 4 , t h e i n d e p e n d e n t c l a s s i c a l p a t h f u r t h e r r e s t r i c t s

its applicationtonearlyhomonuclearoscillatorssuch as CO (and,ofcourse,

a l l homonuclear molecules) colliding with atomic particles o f l i g h t e r mass

t h a ne i t h e ro ft h em o l e c u l a rn u c l e i . The appearanceof a probability

maximum s i g n a l st h ef a i l u r eo ft h et h e o r y .D e s p i t et h e s es h o r t c o m i n g s , we

s h a l l see t h a t t h e Mies s o l u t i o n s t i l l provides a more useful approximation

ofthenumericalpredictionsthantheotheranalyticformulasinvestigated.

91
A convenient form of the Mies r e s u l t w a s g i v e n by e q u a t i o n (4.12)and is

rewritten here for the transition probability from s t a t e m to n, where

n = r n f l as

(5.12)

As withthenumericalmodel,equation(5.12)producesenergy-dependent

transitionprobabilities,while a temperature-dependent r a t e c o e f f i c i e n t is

desired. No a n a l y t i cs o l u t i o no ft h ei n t e g r a le q u a t i o n( 5 . 6 )w i t h P(E)
m
g i v e n by equation(5.12) i s a p p a r e n t ,b u t a r e a s o n a b l ya c c u r a t et e c h n i q u e

(labeledthe "method o f s t e e p e s t d e s c e n t " ) f o r o b t a i n i n g a n a n a l y t i c

approximationk5 i s b a s e d o n t h e w e l l - d e f i n e d maximum contained i n t h e

i n t e g r a n d of equation(5.6). The valueof E a t w h i c ht h e maximum occurs i s

determinedprimarily by theexponentialarguments. The remainingfunction

is slowlyvaryingovertherange of t h e i n t e g r a n d a n d may b e e v a l u a t e d at

t h es i n g l ev a l u e l o c a t i n gt h ep e a k .
E The exponentialargument i s then
P
expanded t o s e c o n d o r d e r a b o u t t h e p e a k a n d t h e term i n t e g r a t e d a n a l y t i c a l l y .

Inthisapplication,thenotation is simplifiedwiththesubstitutions

E E hw /2kT
and T=
I "w L ( ~ / 2 k T ) l / ~ .The e x p o n e n t i anl a t u r e of
mn
equation(5.12) i s a l s o s i m p l i f i e d by n o t i n g t h a t , i n t h e e n e r g y r a n g e w h e r e

t h ep e r t u r b a t i o na n a l y s i s i s a p p l i c a b l e ,t h et r a n s i t i o np e r i o d t = 27r/um
P
i s t y p i c a l l y less t h a n t h e e f f e c t i v e c o l l i s i o n p e r i o d = 2L/U. Thus,
tC

.rrg = t c / t p > 1 andsinh(7rg) % (1/2)eTg.Equations(5.6)and(5.12) are t h e n

combined t o g i v e

92
The integrand peak is located a t

(5.14)

U s i n gt h ep r o c e d u r ed e s c r i b e d ,t h ea p p r o x i m a t es o l u t i o nt oe q u a t i o n( 5 . 1 3 )

(5.15)

where
gP
= E ~ / I T and
P
X
P
= E '(Vm - V ) / ( I T E ~ ~ V ~ ~The
nn
) . e r r o rf u n c t i o ni n

equation(5.15) i s c l o s et ou n i t yf o r mostcases.Equation(5.15)has

log k o! T-1/3 as e x p e c t e da n ds a t i s f i e se q u a t i o n( 5 . 3 ~ ) . The temperature

a t which a g i v e n c o l l i s i o n s p e e d is coincidentwiththepeakoftheintegrand

i ne q u a t i o n( 5 . 1 3 )d e f i n e st h e most e f f e c t i v e s p e e d a t thattemperature;this

temperature w i l l a l s o b e u s e f u l and can be identified from equation (5.14)

as

T = p ~ 3 m a k ~ w m n ~ ~ ) (5.16)
P

Comparisonsof t h ea p p r o x i m a t ei n t e g r a t i o ni ne q u a t i o n( 5 . 1 3 )w i t he x a c t

numericalintegrations show t h a t t h e a p p r o x i m a t e method is most a c c u r a t e ,at

lowtemperatures. The f i r s t - o r d e rp e r t u r b a t i o nf o r m u l a ,e q u a t i o n( 5 . 1 2 ) , is

most a c c u r a t e a t low e n e r g i e s , t h u s f u r t h e r c o n t r i b u t i n g t o t h e a c c u r a c y o f

equation(5.15) a t lowtemperatures.

5.2.3 KernerSolutionforLinearly-Forced Harmonic O s c i l l a t o r s

The f i n a l a n a l y t i c f o r m u l a t o b e c o n s i d e r e d is an exact solution

o b t a i n e d by Kerner36 f o r a h a r m o n i c o s c i l l a t o r t h a t u n d e r g o e s a forcing

93
function linearin the oscillator coordinate. That condition may be satisfied

in situations where r/L << 1 in equation (5.7). The potential may then be

linearized according to

v(ji,r) = A e-ji’L(l - yr/L)

(5.17)

Kerner’s solution was applied Tby

r e a n ~ rin
~ ~a semiclassical collinear

approximation using equation(5.17). Within the framework of the collision

model, the resulting formula exactly calculates the probability of transit

between arbitrary states with the interaction of all states included. Thus,

it can be applied at high collision energies where the interactions of m

than two states influence the oscillator dynamics. Despite the approximate

nature of the harmonic oscillator model, wherein direct multiple-quantum

transitions and the unbalanced coupling of higher and lower states caused

anharmonicity are excluded, the Kerner solution remains useful because it

offers the only analytic means for estimating transition probabilities at

high energies. Examples will be shown where multiple-quantum transitions

and oscillator anharmonicity are not dominant, allowing accurate prediction

by the Kerner solution.

Kerner and Treanor write the probability for transitions between two

arbitrary states m and n as

Pa = m!n!e-EoEh{x J [(-Eo)j(m - j)!j!(n - !

’
-
]
)
j
(5.18)
0
j=o

where J m and n.
is the lesser of the quantum numbers The parameter
EO
is the energy absorbed by
a classical harmonic oscillator divided by one

quantum of vibrational energy. For

a collinear collision and the interaction

of equation (5.17), Rappg6 obtains

94
 (5.19)

where is the reduced mass of the oscillator and w is the oscillator

frequency. The accuracy of the model, when applied to'highly excited

oscillators, is substantially improved if the effective oscillator frequency

is corrected for anharmonicity for each initial state

m according to

w = we(l - 2xem). Without the correction, the excited-state rate coefficients

(5.1),
would simply behave according to the Landau-Teller relation, equation

at low temperatures where the effective values Eof

0
are all less than

unity and give k

m,m- 0
< 1 for large E
0
.
An inconvenience of the

Kerner formula is its incompatibility with the approximate integration method

of equation( 5 . 6 ) for obtaininga rate coefficient. A simplified versionof

equation (5.18), assuming E0 << 1, permits an approximate analytical

to a thermal range
solution. However, the calculations are then restricted

where multiple-quantum effects are insignificant and the theory loses its

advantages over perturbation solutions. In the comparisons to follow, we

have therefore resorted to ( 5 . 6 ) when

a numerical integration of equation

the Kerner solution is applied.

5.3 Comparisons with CO-He Experiments

In this section, the ability of the theoretical model to reproduce

experimental rate coefficients is tested. Unlike past comparisons of

vibrational rate coefficients with theory, we now have access to at least

state^.^
one setof experimental values for excited initial To test the

consistency of the theory and experiment for all vibrational states, however,

the effective interaction range L and the hard-sphere cross sectionu0

95
are determined from the abundant collection of measurements dominated by

transitions between the ground state and first vibrational state. The

interaction parameters required to match the ground-state experiments are

then applied in comparisons with the excited-state rate measurements.

5.3.1 Effective Interaction Potential Parameters

The computational convenience gained from the simplified interaction

potential I, equation (5.7), justifies its use, but

as a consequence of its

simplified form, the predicted rate coefficients cannot be expected to

reproduce the experiments at all kinetic temperatures. Transitions induced

in an oscillator depend to a large extent on the potential gradient near

the distance of closest approach; while in a collinear collision, the dist

of closest approach is determined solely by the coordinate where the poten-

tial magnitude equals the initial kinetic energy of the collision. Thus

both potential features are important. However, the magnitude of a purely

(5.7), and that of a more realistic

repulsive potential, such as equation

potential with an attractive well may be the same at the closest approach

distance, but have a significantly different gradient. Consequently, where

collisions are averaged over a range of energies, the predicted variation

of rate coefficients with kinetic temperature be

will
different for the

two potentials. By matching theory and experiment in several thermal

of the
ranges, and by using more than one potential form, an indication

degree of uncertainty in rate coefficients attributable

to potential errors

can be obtained. For that purpose, we consider a second potential given by

(
x
,
"
) /L (xe-x>/2L
VII(x) = D e - 2D e (5.20)

96
Potential I1 is a Morse-type interaction with an attractive well of depth

-D at coordinate x
e
. As with equation (5.7), the exponential form allows

matrix elements to be calculated analytically.

Predictions by the numerical anharmonic oscillator model with the

oscillator initially in the first eigenstate= m1 are compared with

experiment in figure5.1. When potential I, equation (5.7), is used, the

A, so that only the range

rate coefficients are independent of the magnitude

L requires specification. Similarly, the predictions using potentialI1

are independent of x but require both L and D to be specified. The value

e’
D/k = 100 K is representative of well depths inferred from viscosity

measurements.80 The two potential gradients are different by 20

about
percent

at closest approach for the typical conditions considered. Figure 5.1

demonstrates the expected results.No unique set of potential parameters

reproduces the experiments over the complete thermal range, but the more

realistic potential I1 comes the closes. The required values of L fall

between 0.02 and 0.03 nm, depending on the thermal range considered.

A s an interesting aside, note that the low-temperature departure of

the experimental rate from a variation proportional to T-’I3 is also

followed by the theory using simple repulsive potentials.

As Shing7 points

out, these low-temperature departures do not necessarily on

depend
weak

attractive forces normally omitted from the interaction potential; they even

occur with a repulsive potential when the thermal averaging integration is

done accurately for low collision energies. We know, however, that real

interaction potentials usually contain an attractive component and it will

augment this low-temperature behavior.

97
 3000 IO00 500 300 200 1 0 0
-I2r A I I I I I

-13 1
L = O . O ~ nrn
0
3 -I6 1 ,L = 0.03 nrn, o/k = 1 0 0K

Figure 5.1.- A comparison of experimental rate coefficientsCO(M for= 1)-He

transitions to the ground vibrational state with predictions from the
numerical model of chapter 4 . The solid and long-short dashed lines
were computed using the repulsive interaction potential I, equation
(5.7). The short-dashed line was computed using the Morse interaction
potential 11, equation (5.20). Hard-sphere collision cross sections
were chosen for each potential to match the experiment T = 1000
at K.
Experimental values are from:o reference 16, reference 17a,
A reference 17b,+ reference 17c.

5.3.2 Comparisons with Excited-State Rate Measurements

Normalized rate coefficients, predicted for initially excited

CO at

T = 300 K, are compared in figure 5.2 with the room temperature measurements
of Hancock and Smith.
l8 The parameter k is much less sensitive
m,m-l’*l, o
to interaction uncertainties than the absolute rate coefficients and varies

in a simple, nearly linear manner with initial-state quantum number m.

The nearly linear quantum-number dependence, increasing with

m at room

temperature, is predicted for all the interaction potentials examined and is

As figure 5.2
believed to be an accurate description of the real behavior.

98
 I

L L = 0.03 nm, /
/

0.11 I I I J
0 5 IO 15 20
INITIAL-STATEVIBRATIONALQUANTUM No., m . -

Figure 5.2.- A comparison of experimental rate coefficients T = 300

at K for
CO(m)-He transitions from vibrational states m to m - 1 with predictions
from the numerical model using repulsive potentialI, equation (5.7). The
excited-state data are from reference18 and have been normalized using
the experimental k1,o value of Mil1ikenl6,’’ (fig. 5.1).

shows, the experimental excited-state values compare favorably in magnitude

with the predictions, but their trend is inconsistent with a linear extrapo-

lation to m = 1. A highly nonlinear extrapolation is contrary to any

prediction of the collision model at any temperature. Although the

collision model contains many simplifications awaiting refinement, the

behavior implied by the experimental rates appears to
also
require further

verification and extension. In the interim, the theoretical predictions

of excited-state rates seem to be qualitatively reasonable and self consistent

Zespite their quantitative uncertainty. Unfortunately, their verification

by experiment remains inconclusive.

5.4 An Evaluation of the Analytic Approximations

The computational expense of the numerical model makes it impractical as

a general means of estimating excited-state rate coefficients. Instead, it is

99
used here as a basis for evaluating the more convenient but less complete

analytic formulas. The predicted rate coefficient variations with quantum.

in figure5.3 for two extreme

nuniber for several models are illustrated

temperatures. The differences in the various models depend strongly on the

kinetic temperature, but they all predict a simple monotonic change with

quantum number. The analytic approximations are therefore more clearly

evaluated by choosing the highest initial quantum number of practical interes

and then comparing the predictions for a range of temperatures. For CO,

T=300K

T = 3000K

0 5 10 15 20
INITIAL-STATE VIBRATIONAL QUANTUM NO., m

Figure 5.3.- The CO(m)-He rate coefficient dependence on quantum number

predicted by several collision models. The solid lines represent the
anharmonic numerical model, the long-short dashed lines represent the
Kerner harmonic oscillator solution,36 equation (5.18), and the dashed
9 4 equation (5.8).
lines are from the formula of Keck and Carrier, The
potential range L = 0.02 nm was used in all cases.

Rich e t aZ.15 have shown that energy transfer from vibrational levels as

high as the twentieth can influence the net energy balance in an electricall

excited CO laser system. Choosing m = 20 as an example, the single-quantum

rate coefficients predicted by all the collision models are compared

100
in figure 5.4. The independent parameter @we/kT) was chosen so that
predictions by the Keck-Carrier formula, equation (5.8), appear as a nearly

straight line. A comparison of the rates from the numerical model using

T, K
3000 1000 500 300 200
I I I I I

KECK-CARRIER EQ. (5.8) /

7 KERNER

D/k 100 K

Figure 5.4.- A comparison of excited-state rate coefficients for

CO(m = 20)-He predicted by several collision models. The potential
range was L = 0.02 nm in all cases.

potentials I and I1 shows the moderate sensitivity of

k
m,m-l'*l, o to the
L at all temperatures. Not
form of the potential for one potential range

shown is the great sensitivity

of the magnitudeof km,m-l'*l, 0 to other
potential ranges at any temperature. Note, however, that the qualitative

nature of the predictions are undisturbed form of the potential and

by the

are therefore considered realistic.As expected, the Mies solution,

equation (5.15), accurately reproduces the numerical results at low tempera-

tures, but fails at higher temperatures where multiple-state interactions

begin to affect the single-quantum transitions. The departure is signaled

when transition probabilities approaching unity influence the thermal

101
a v e r a g i n gi n t e g r a l ,e q u a t i o n (5.6). S i n c e CO i s notveryanharmonic,the

Kerner harmonicoscillatormodel,equation(5.18),frequency-correctedfor

anharmonicity a t m = 20,works w e l l o v e rt h ee n t i r et h e r m a lr a n g e .N o t e

that the anharmonic correction must be included, however, as a l l p r e d i c t i o n s

are s i g n i f i c a n t l y a b o v e t h e r e s u l t s t a t e d by e q u a t i o n (5.1) f o r a s i n g l e -

f r e q u e n c yh a r m o n i co s c i l l a t o r .F i n a l l y ,f i g u r e 5.4 shows t h a t t h e Keck-

Carrier formula,equation (5.8), i s t o oc r u d ea na p p r o x i m a t i o nf o rl a r g e

i n i t i a l quantum numbers.

The d e g r e e o f o s c i l l a t o r d i s t o r t i o n c a u s e d by t h e c o l l i s i o n of a l i g h t

helium atom with a CO m o l e c u l e h a s a n i n s i g n i f i c a n t e f f e c t o n t h e classical

t r a j e c t o r y .T h i sf a c t is made e v i d e n t by t h e small d i f f e r e n c e a t low

temperaturesbetweenthenumerical model(where the effect i s included)and

t h e Mies s o l u t i o n (where i t i s neglected). An example i n whichthecoupling

is larger is i l l u s t r a t e d i n f i g u r e 5.5 f o r CO(m = 20)-Ar c o l l i s i o n s . I n t h i s

T, K
3000 1000 500 300 200
1000 r I I I I I

KECK-CARRIER EQ. (5.8)

NUMERICAL
MODEL

0 100
”-”
-
1
E
\

i
IO

F i g u r e 5.5.- A comparison of e x c i t e d - s t a t e r a t e c o e f f i c i e n t s f o r
CO(m = 20)-Ar. P o t e n t i a l I , e q u a t i o n (5.7), w a s usedwith
L = 0.02 nm i n a l l c a s e s .

102
situation, none of the analytic models do well at low temperatures because

the effects of oscillator distortion on the classical path modifies the

transition probabilities even near threshold. The small corrections are

then greatly amplified by the thermal averaging integral at low temperatures

The.smal1anharmonicity of CO(xe = 0.0062) has influenced the preceding

examples mainly by altering the energy spacing between excited eigenstatea.

Anharmonicity also modifies the absolute magnitude of the rate coefficients,

An example in which the

but that effect is not apparent in km,m-l/mkl,o.

5.6 for H2(m = 10)-He

anharmonicity is large is illustrated in figure

(xe = 0.0268). In this case, the frequency-corrected harmonic oscillator

model is inaccurate at all temperatures. The large spacing between eigen-

energies in H suppresses the onset of multistate interactions

2

0 100 I

MODEL
I I I I I
0 I 2 3 4 5 6

Figure 5.6.- A comparison of excited-state rate coefficients for

HZ(m = 10)-He. Potential I, equation (5.7), was used with
L = 0.02 nm in all cases.

103
at high temperatures, making the Mies solution
an accurate reproduction
of

the numerical results over the entire thermal range. The difference
mass in

between theHe and H nuclei produces only moderate coupling between the

fig. 4.2).
compressed oscillator and the classical path (e.g., see

As the preceding comparisons indicate, one cannot generally choose

a

single analytic model for estimating excited-state rate coefficients that

is applicable to all collision pairs. The situations where

a model should

not be used are easier to identify. Clearly, the Keck-Carrier formula,

equation (5.8), is too approximate in all the examples. The Kerner harmonic

oscillator solution, equation (5.18), with anharmonicity-corrected frequen-

cies is reasonably accurate unless the anharmonicity is large. The Mies

anharmonic oscillator solution, equation (5.15), isa poor approximation

when multiple-state interactions become important. Finally, no analytic

model based on the semiclassical approximation will be realistic when the

oscillator dynamics have

a significant influence on the classical of
path

the incident particle. This restriction limits all the models considered

to collision pairs in which the mass of the incident particle is not

significantly greater than the mass

of the impacted nucleus and to oscilla-

tors that are not extremely heteronuclear.

5.5 Multiple-Quantum Transitions

In the preceding section, only transitions to an adjacent state were

examined. Here, we investigate the relative importance of multiple-quantum

transitions, particularly for oscillators in highly excited states. The

5.7
probabilities of multiple-quantum transitions are compared in figure

both for CO(m)-He collisions in which the oscillator is initially in an

104
 EFFECTIVETEMPERATURE,Tp, K FROM EQ. (5.16)
300 1000 3000 5000
I I I I

m--n = 20-19

) 2 4 6 8 IO 12
RELATIVE COLLISIONSPEED, i,kmlsec

Figure 5.7.- Multiple-quantum transition probabilities for CO(m)-He

I and
collisions using the anharmonic numerical model with potential
L = 0.02 nm. The effective temperature Tp locates the most effective
collision speed contributing to the thermally averaged rate coefficient
at the temperature designated.

excited state and in states near the ground state. The collision speeds

contributing most to the thermally averaged rate coefficient

a selected
at

temperature are indicated by the effective temperatureT In the thermal

P'
range considered, multiple-quantum transitions to the ground state are always

improbable compared to single-quantum transitions from the first vibrational

level, but the situation is clearly different when the oscillator is

initially in the twentieth quantum state. However, thermally averaging the

transition probabilities in figure 5.7 reduces the apparent importance

of

multiple-quantum transitions in a relaxation process. Figure 5.8 illustrates

I
two potential ranges, using potential
the resulting rate coefficients for

and values of cro obtained from the experimental match in figure 5.1 at

T = 1000 K. The amplified uncertainty caused by the interaction potential

105
 -11 -
- - -12
8
2 -13 -
E V

5 -14 -
E
Y
2 -15 -
(3

3 -
-16

-I7
-18 I
.04
t I
.06
I
.08
I
.IO
I
.I2
\
\
\

.I4
\

I
\

.I6
I I
.I8
T"'3 (K)

Figure 5.8.- Multiple-quantum rate coefficients for CO(m)-He. Potential I

was used in the anharmonic numerical model. The hard-sphere cross-section
values a0 for each potential range are those required to match the
experimental rates in figure 5.1 at T = 1000 K.

and its influenceon the implied value ofuo is most obvious, but the

qualitative features are again consistent for both potential ranges. For

oscillators like CO, multiple-quantum transitions provide

a significant

path for energy transfer only at very high temperatures according to these

predict ions.

A temperature marking the onset of competitive multiple-quantum

transitions is the characteristic vibrational temperature of the oscillator,

here defined as 8 = fiwe/k (for CO, 8 = 3122 K). An oscillator in which

V V
multiple-quantum transitions will dominate the relaxation process can then b

identified if BV is small compared to the thermal range

of interest. One

extreme example is Br2 for which BV = 465 K. Since the anharmonicity is

also small in Br2(xe = 0.0033), the Kerner harmonic oscillator model has

106
I

been used to obtain the Brp-He rate coefficients displayed 5 in

. 9 . figure

Two- and three-quantum transitions from the tenth vibrational level are

shown to be significant even at room temperature, and the temperature

dependence of the single-quantum rate (m + n = 10 + 9) is invertedby

multiple-state interactions when compared with the dependence shown in

figure 5 . 8 . in this
The high probability of multiple-quantum transitions

case contributes to the extremely fast and thermally insensitive relaxation

a single
rates measured in the halogens and it destroys the ofconcept

the
"relaxation time" that is independent of the nonequilibriumof state

process for molecules of this type.

Figure 5 . 9 . - Multiple-quantum rate coefficients for Br (m)-He predicted

using the Kerner harmonic oscillator solution, equatfon (5.18), with
L = 0.02 nm.

5.6 Concluding Remarks

We have relied aoncollinear semiclassical model for vibrationally

inelastic collisions entirely for pragmatic reasons. The collinear geometry

107
 affords an economically reasonable means of e s t i m a t i n g V-T rate c o e f f i c i e n t s

for excited molecules and the semiclassical approximation is easilyreduced

t op r a c t i c a la n a l y t i cs o l u t i o n s . While t h e s e s i m p l i f i c a t i o n s c l e a r l y

obviatethequantitativeaccuracy of t h e c a l c u l a t i o n s , n o s e r i o u s o m i s s i o n

other than rotational coupling i s apparent that wouldmodify their qualitative

n a t u r e ,e v e ni nt h ep r e s e n c eo fu n c e r t a i ni n t e r a c t i o np o t e n t i a l s .U n f o r t u -

nately,anattempttoconfirmthepredictedfeaturesthroughexperimental com-

parison was inconclusive. However, t h ee x p e r i m e n t a lc o n d i t i o n st h a t would

t e s t t h e modelmost s e v e r e l yc a n a t l e a s t beidentified.Forexample,the

c h o i c e of c o l l i s i o n p a r t n e r h a s a l a r g e i n f l u e n c e on t h e rate c o e f f i c i e n t s e n -

sitivitytoinitial quantumnumber.Note t h el a r g ed e v i a t i o n s of k
m,m-l /mk 1 , 0
from u n i t y i n f i g u r e 5.5 f o r CO-Ar compared t o t h o s e i n f i g u r e 5.4 f o r Co-He.

Furthermore,theincreasedoscillatordistortioncausedbyheavy atomimpact

r e q u i r e s a more c o m p l e t e d e s c r i p t i o n of t h e i n t e r a c t i o n t h a n n e e d e d f o r l i g h t

atoms. From a n o t h e rv i e w p o i n t ,t h e lesser s e n s i t i v i t y of some f e a t u r e s of t h e

predictiontouncertaintiescanguidethechoice ofexperimentalvariablesto

beemphasized. I np a r t i c u l a r ,a na p p a r e n t l yu n i v e r s a lf e a t u r e of t h e V-T

e x c i t e d - s t a t e rate p r e d i c t i o n s i s t h e i r monotonic low-order variation with

quantumnumber. Once t h i s f e a t u r e i s confirmed,theexperimentalemphasis

can be shifted t o t h e less p r e d i c t a b l e v a r i a t i o n s w i t h k i n e t i c t e m p e r a t u r e .

F i n a l l y , a comparisonofthe estimates u s i n g v a r i o u s p o t e n t i a l p a r a m e t e r s

suggeststhat a s e l f - c o n s i s t e n t set of experimental rates f o r b o t h h i g h and

low i n i t i a l quantumnumbers c o n t a i n s much more i n f o r m a t i o n t h a t d e f i n e s t h e

interaction potential than ground-state rates a l o n e .

Comparisonsof the analytic andnumerical rate c o e f f i c i e n t s g r a p h i c a l l y

d e l i n e a t et h es u i t a b l er a n g e of a p p l i c a t i o n f o r e a c h a n a l y t i c model.However,

108
the utility of an analytic approximation can also depend on the physical

p r o p e r t i e so ft h ea p p l i c a t i o n .F o re x a m p l e ,t h eK e r n e rh a r m o n i co s c i l l a t o r

model,
with
anharmonically
corrected
frequencies,
predicts k m
/k
m,m-1 1 ,o
with surprising accuracy for many m o l e c u l e s ; b u t b e f o r e t h e model c a n b e

economicallyapplied,ananalyticalsolutiontothethermalaveraging

integral,includingKerner'stransitionprobabilityformula, awaits develop-

ment. Even w i t h t h a t s o l u t i o n i n hand,onemustbeconcernedwiththeeffect

of a n h a r m o n i c i t yf o re a c hm o l e c u l et r e a t e d by t h e model. On t h e o t h e r h a n d ,

Mies' s o l u t i o n f o r a n h a r m o n i c o s c i l l a t o r s , e q u a t i o n ( 5 . 1 5 ) , f a i l s a t high

temperature. A t t h o s ec o n d i t i o n s , however, many nonequilibriumprocesses

are i n s e n s i t i v e t o t h e V-T r a t e s of e x c i t e d s t a t e s , e i t h e r b e c a u s e t h e v i b r a -

t i o n a l s t a t e p o p u l a t i o n d i s t r i b u t i o n i s n e a r l y Boltzmann o r b e c a u s e t h e

process i s c o n t r o l l e d by some s e p a r a t ee n e r g y - t r a n s f e r mechanism. A t lower

temperatures,the model a c c u r a t e l y d e a l s w i t h a broader range of oscillators

becauseanharmonicity i s r i g o r o u s l yi n c l u d e d .C o l l i s i o np a r t n e r sf o rw h i c h

the theory fails are poorly treated by a l l t h e a n a l y t i c s o l u t i o n s b a s e d on a

semiclassical approximation.Similarly,thefrequentlyusedformula

developed byKeck and Carrier i s u s e f u l b e c a u s e o f its simplicity, but the

additional computation required by t h e Mies s o l u t i o n i s n o t p r o h i b i t i v e .

The series f u n c t i o n O(-g,X) c o n v e r g e sr a p i d l ya n dt h em a t r i xe l e m e n t s

may be,computed i n advance.

Calculationsofmultiple-quantumtransition rates from excited states

validate the assumption most often made i n k i n e t i c models of nonequilibrium

p r o c e s s e s :t h e yc a nu s u a l l yb en e g l e c t e d . A s b e f o r e , a t veryhightempera-

tures where multiple-quantum transitions become c o m p e t i t i v e , a nonequilibrium

process i s u s u a l l y n o t c o n t r o l l e d by e x c i t e d - s t a t e V-T rates, w h i l e

109
ground-state transitions are s t i l l dominated by single-quantum steps.

Molecules with closely spaced vibrational energy levels, such a s thehalogens,

are notable exceptions requiring a more careful analysis.

110
 CHAPTER 6

EFFECTS OF ROTATIONAL TRANSITIONS ON VIBRATIONAL ENERGY TRANSFER

The preceding chapters have utilized

a collinear collision model in which

vibrational motion was the only

form of energy transferred during
a collision,

and, indeed, in many cases it is. However, the use

a one-dimensional
of col-

lision geometry renders the model incomplete in the sense that cross sections

and rate coefficients cannot be obtained directly, but require artificial

three-dimensional parameters such as steric factors or hard-sphere cross

sections that must be estimated by some other means.

From a more physical point of view, collisions with sufficient t oenergy

induce vibrational transitions will simultaneously cause numerous transitions

among the more closely spaced rotational states, thus invoking an additional

energy sink not represented in the collinear models. This chapter investi-

gates the influence of rotational motion on the net rate of vibrational ene

transfer. It is motivated bya need to assess the validity of the collinear

models since they remain the most practical means for predicting vibrational

rate coefficients ina kinetic analysis. With that motivation, emphasis is

directed here toward the net rate of vibrational energy transfer summed oqer

all final rotational states, rather than individual vibration-rotation transi- *.-

tional rates, since only the former can be compared with the collinear

predictions.

In the sections to follow,

a semiclassical three-dimensional collision.

It is followed bya description of some

model is first developed in detail.

approximations that significantly reduce the number of coupled states neces-

sary to obtain
a complete solution, thus making numerical results practical.
The collision dynamics are then studied for molecular types that represent

extremes in the role of rotational motion on vibrational transition rate

The role of rotational coupling is summarized and categorized in conceptu

terms in the final section and the common characteristics

of all related V-R-T

mechanisms are discussed. .

6.1 Vibration-Rotation Collision Model

A three-dimensional, vibration-rotation collision model is formulated

here within the semiclassical framework described in B and based on

appendix

the following underlying concepts: the incident particle is considered struc-

tureless while the target is a diatomic heteronuclear molecule.

A natural

parameter for measuring the heteronuclear nature of the moleculemass

is its

ratio

Y = mc/(q, + mc>
where % and mc are the nuclear masses and mc 2 q,. The inertial proper-

ties of the molecule are modeled Morse-oscillator/rigid-rotor

by a description

(discussed in ch. 3 ) . The collision geometry is described classically

3 . 4 as viewed in a rotating
with the associated coordinates shown in figure

interaction plane containing all three nuclei. The classical trajectory is

assumed to be dominated by the spherically symmetric component

of the interac-

tion potential and is determined from just those terms. Consequently, the

relative path remains in a single plane and the subsequent formulation is

greatly simplified. These concepts are reflected in an illustration of the

collision geometry shown in figure 6.1, where it is viewed from a space-fix

position in a center-of-mass reference frame aligned with the plane of the

trajectory.

112
 'TRAJECTORY \ii
-
PLANE
Figure 6.1- Three-dimensional encounter nomenclature and geometry as viewed
~

from a fixed position in the center-of-mass reference frame. x',y'

The
plane contains the molecular mass center and the incident particle path.
Only the portionof the molecule above the plane is shown.

The detailed formulation of a semiclassical model divides logically into

three main - one

parts defining the nature
of the interaction potential

between the colliding pair, one detailing the quantized motion of the molecu

in response to a time-dependent disturbance, and one describing the classical

motion of the incident particle that produces the disturbance. The descrip-

tion to follow proceeds in the same order.

6.1.1 Interaction Potential

A comparison of the predictions from the collinear model described in

chapter 4 with those of a three-dimensional model will be most meaningful

if

the interaction potentials are similar. We therefore make use of the expo-

nentially repulsive and pairwise additive interaction discussed in 3 chapter

3.4,
and write, with reference to figure
 .. . "
"

To c o n v ean i e n t l y s e p a r a t e t h e m o l e c u l a r d y n a m i c s f r o m t h e c l a s s i c a l m o t i o n , '

h o w e v e r ,e q u a t i o n( 6 . 1 )m u s tb ee x p r e s s e de x p l i c i t l yi n terms of c o o r d i n a t e s

d e s c r i b i n g each of the m o t i o n ss e p a r a t e l y . To t h i s end, we have shown i n

c h a p t e r 3 t h a te q u a t i o n( 6 . 1 )c a nb er e p r e s e n t e dt of i r s t - o r d e ri n r/Z by

w h e r et h er e l a t i v ea n g l e , 6 , is r e l a t e d t o t h e s p a c e - f i x e d c o o r d i n a t e a n g l e s i n

figure 6.1 by

cos 6 = s i n 8 cos($ - -52) (6.3)

E q u a t i o n( 6 . 2 )e x p r e s s e st h ep o t e n t i a li nt h ed e s i r e de x p l i c i t form. However,

to aidthefollowingseparationofdynamicalequationsintocoordinatesthat

describethemotionofeachcollisionpartner, we s h a l l t e m p o r a r i l y d e n o t e t h e
-t + +
p o t e n t i a l by a ne q u i v a l e n tn o t a t i o nV ' ( E , r , 6 ) E V'(q,t)where q = q(r,f3,@)

l o c a t e st h em o l e c u l ei nc o n f i g u r a t i o ns p a c e and t emphasizesthetemporal

d e p e n d e n c eo ft h et r a j e c t o r yc o o r d i n a t e s , Z ( t ) and G ( t ) , a p p e a r i n g i n equa-

tions(6.2)and(6.3).

6.1.2 QuantizedMolecular Dynamics

I n appendix B, w e show t h a t t h e q u a n t u w m e c h a n i c a l e q u a t i o n o f m o t i o n may

be reduced to a set o f d i f f e r e n t i a l e q u a t i o n s - one f o r e a c h bound e i g e n s t a t e

o f the uii'dtisturbed molecule - in'terms of the probability amplitudes associated

w i t he a c h bound s t a t e . The r e s u l t i s

where t h e b r a c k e t n o t a t i o n r e f e r s t o

114
 +
integrated over all q space and $n is an eigenfunction of the undisturbed

molecule determined by the intramolecular potential,

Vo(r). As in chapter4,
1
the intramolecular potential is modeled by the Morse function:

Combined with a rigid-rotor description of the molecular rotational motion,

the eigenfunctions $n are then determined by thrse Guantum numbers IvRm)

and have their eigenfrequency given by

wVll = + +)- + +)*+ BeR(R + 1)

(6.4), is then to evalu-
The remaining task, leading to solutions for equation

ate the matrix elements defined by equation (6.5) in terms of the fundamental

collisional and molecular parameters.

The numerical labor of solving equation (6.4) will be reduced greatly if

the matrix elements can be factoreda into

time-dependent term obtained classi-

cally and state-dependent terms containing all the quantum-mechanical spatial

integrals. The spatial integration may then be completed independently and in

step in
advance for transitions between all eigenstates in the basis Aset.

that direction is taken by writing

(j/V'(G,t)ln) = U(b,t)Vt
(t) (6.8)
jn
where, from the potentia1,given by,equation
(6.2), the right-hand termsa m 7.<.

-%(b, t) /L
U(b,t) = A e (6.9)
and

(6.10)

with a1 = Y and a2 = -(1 - Y). Clearly, the function U(b,t) can be

V!Jn(t)
obtained classically, but the expression for must now be developed to

115
 . ... . ..

furtherisolate i t s time dependence. A u s e f u l a i d w i l l b et h ee x p a n s i o no f

z cos 6
e i n terms Legendre
of polynomials
PJ(c0s 6) given by equation
(3.30).

Inthepresentnotation,theexpansion is

e
a
r
-
i L
cos 6
= 5(%)
J=0
J
(25 + 1)iJ(ai z> pJ(cos 6 ) (6.11)

whereiJ(air/L) i s a s p h e r i c a l Bessel f u n c t i o no ft h ef i r s tk i n d . 73

R e c a l l i n gt h a tI n )r e f e r st o a v i b r a t i o n - r o t a t i o n s t a t e w i t h quantum

numbers IvRm) and t h a tt h em o l e c u l e i s r e p r e s e n t e d as a M o r s e - o s c i l l a t o r /

r i g i dr o t o r ,t h ee i g e n f u n c t i o n sr e p r e s e n t e di ne q u a t i o n (6.10) may b e f a c t o r e d

in the traditional manner a c c o r d i n g t o

q r )
$vRm(r'8, @ )= ___ (6.12)
r YRm@ ,9)

The f a c t o r i z a t i o n , i n c o n j u n c t i o n w i t h e q u a t i o n ( 6 . 1 1 ) , t h e n a l l o w s t h e matrix

elements to be represented as a sum ofproductsgivenby

(J) (J)
vf: E'm'vRm ( t ) = (25 + l>RvIv TRImIRm (6.13)
J=0

where

(6.14)

i s a matrix
radial
independent
of time and , . . _ L

(J) ( t ) = (R'm' 1pJ(cos 6 ) I R m ) (6.15)

T~ 1 m I Em
-
i s a s p h e r i c a lm a t r i xe l e m e n tc o n t a i n i n gt h et r a j e c t o r yc o o r d i n a t eQ ( t )v i a

e q u a t i o n( 6 . 3 ) . The r e m a i n i n gd i s c u s s i o n i s d i v i d e di n t os e p a r a t ed e v e l o p -

mentsofeachelement.

116
6.1.2.1 Radial Matrix Elements
(6.14) appears in expanded
The radial term defined by equation form as

= 1/2), the radial

First note that when the molecule is homonuclear Y (i.e.,

and that it will emphasize

term will be nonzero only for even valuesJ of

even J values for most heteronuclear molecules whereY is nearly 1/2.

This property directly affects the probabilities

of rotational transitions.

(6.16) in terms of the

To evaluate the spherical Bessel functions in equation

molecular coordinate r, we note that its arguments lie typically in the range

0 5 air/L ,< 5. Larger values are suppressed by the vibrational eigenfunctions

that approach zero at large r. In this rangeof arguments, the spherical

Bessel functions may be calculated with rapid convergence by the ascending

iJ(Z) =
J
Z
J
['
+
2212
(25 + 32)! +- (25
(2212)
+ 3)(2J + 5)
+.. .] (6.17)
II (2j + 1)
j=O

The radial matrix element may be

then
written as

j= O k= 0

(m)
wherer v'v represents the remaining simplified integral

(6.19)

Equation (6.19) is similar to the integrals that define dipole matrix elements

associated with vibrational band intensity calculations and, as such, it has

been solved exactly for m= 1 and 2 using Morse oscillator

117
eigenfunction~.~
In~ ~principle,
~~ the integral can be solved exactly for an

integer valueof m, but the complexity of the solution increases and become

impractical for powers larger than =m 2. An iterative numerical method has

O 0 but it becomes laborious for large quantum numbers.

also been developed,

In appendix C, we derive an approximate closed-form solution to equa-

tion (6.19) with the result:

V'SY
r (m) = Nv' v
v' v
Dsr(A + s + 1) (6.20)
(aL)m s=o

where k' = ue/uexe, A = k' - 2 - (v' + v), and I'(A + s + 1) is a gamma func-

tion.73 Coefficients Ds and NVlv contain elements of the Morse eigenfunc-

tions (defined in appendix

C). The derivation of equation (6.20) depends only

on the provision that A >> 1, which is easily obtained becausek' >> 1 for

all diatomic molecules. Typical values of k' range from 37 forH2 to 161 for

CO.Correspondingerrorsinfromequation(6.20)are1.5percentfor

H p and 0.3 percent for CO. Hence equation (6.20) is sufficiently accurate in
this application, although some numerical difficulties arise that can limit

use. For example, the termsof the summation in equation (6.20) alternate in

sign so that, for large k' and large vibrational quantum numbers, small dif-

ferences between extremely large terms cause the loss of all significant di

The CDC-7600 computer with 28 digits in double precision allowed equation (6.

to be evaluated with at least 3 accurate digits for vibrational quantum num-

bers less than12 when k' = 161 and for all quantum numbers to the continuum

when k' = 37. In the few cases when equation (6.20) could not be used, the

integral was evaluated with a standard Gauss-Laguerre quadrature algo-

rithmlo1-lo3of very high accuracy. (The author is indebted to D. G. Galant,

NASA Ames Research Center, for developing the algorithm.)

118
6.1.2.2 Spherical Matrix Elements

where L is the orbital angular momentum operator andL, is a component.

Note that the Legendre polynomial in equation (6.15) can also be represented

as a spherical harmonic according to

PJ(C0S 6 ) = 4- yJ,o(6,0)

allowing the spherical matrix element

to be written as

The solution to equation (6.21) follows common procedures in the mechanics

of

quantized angular momentumlo4

9 lo' and it is described in detail in D.
appendix

The result takes the form

where the time-independent term is

(6.23)

Nonzero values are obtained only if

(6.24)

119
The bracket symbols in equation (6.23) are Wigner 3-j symbols that account

for the vector coupling between the angular I

momentum Rstates,
'm' ) and I Rm),
and the trajectory orbital momentum designated by J. They impose further

constraints associated with nonzero values A (J)

of that are col-
listed
R 'm' km

(6.25)

6.1.2.3 Complete Factored Matrix Elements

Factorization of the time-dependent terms in the complete matrix element

time-a
defined by equation(6.8) can now be accomplished by defining

independent matrix element (with an unprimed symbol) as

(6.26)

and writing the complete matrix element as

-% -i(m'-m)z(b,t)
(v'R'mlV' (q,t) IvRm) = U(b,t)e (6.27)
'v' R'rn'vRrn

The time-dependent terms, U(b,t) and E(b,t) , in equation (6.27j are then
the functions required from the classical trajectory. Generally, they repre-

sent both an induced force and an induced phase shift in the molecular mo

where the magnitude of the latter depends on the rotational transition con-

sidered. However, the primary quantal properties of the collision dynamics are

determined by the time-independent matrix elements given by equation (6.26).

For example, the summation limits in equation (6.26) reflect the constraints

imposed by equations(6.25) and lead to the only significant selection rule

(6.16)
associated with vibration-rotation transitions. Recall from equation

120
 R(J)
that, for homonuclear molecules,
v v J is even. Thus,
is nonzero only when

nonzero matrix elements and transition probabilities for homonuclear

willvoccur

molecules only when 111' - 1 1 1 is even, according to equation ( 6 . 2 6 ) . Simi-

of even
larly, for heteronuclear molecules, transitions la' - El will domi-

nate, although odd-increment quantum changes are allowed in those molecules.

Other selection rules regarding intermultiplet transitions,

m' to m, are also

implied by equation( 6 . 2 5 ) and their accompanying zeros may be observed in

table 6.1, where a typical transition matrixis listed. However, the roleof

these degenerate states in determining the observable behavior

of a kinetic

l o s t due to subsequent averaging and hence become important

process is usually

aspects of t h e collision model.

only in the computational

Figures 6 . 2 and 6 . 3 illustrate some general properties

of the time-

independent matrix elements and allow one tosome early

reach conclusions con-
Figure 6.2- Variation of time-independent matrix elements defined
by equa-
CO with v = 0,
tion (6.26) with angular momentum quantum numbers, for
v' = 1, and L = 0.02 nm.

0 1=0
0 1 =I
0 1=20
10-1

. ,

10-eo
2 4 6 8 IO
A1

Figure 6.3.- Variation of time-independent matrix elements withA R = 111' --d 1,

for H, and CO with v = 0 and v' = 1.
,. . 1 '.

122
 0 z=o
01.5
0 Z=40
10-1

(b)
I I I I 1
10-4
0 2 4 6 0 10
A1

Figure 6 . 3 . - Concluded.

example, f i g u r e 6.2 d e p i c t s t h e v a r i a t i o n o f m a t r i x e l e m e n t s w i t h p r o j e c t i o n

s t a t e quantumnumber.These f e a t u r e s w i l l b eo fi n t e r e s t l a t e r when methods

f o rr e d u c i n gt h e number ofcoupled states i n t h e c a l c u l a t i o n are sought. At

thispoint, we simplynotethattransitions from t h e c o r n e r s where m = fR,

m' = + a ' , and m', m havethe same s i g n a r e t h e dominant r o u t e by whichenergy

is t r a n s f e r r e d . As 11 and 11' i n c r e a s e ,t h e dominance a l s oi n c r e a s e s so t h a t

in t h e l i m i t o fl a r g e 11, a ' , a l l o t h e r m f: 211 and m' f 211' states may b e

ignored.

Another b a s i c a s p e c t o f t h e m a t r i x e l e m e n t s is i l l u s t r a t e d i n f i g -

u r e s 6.3(a) and (b) where for both H2 and CO - two e x t r e m e l y o p p o s i t e m o l e c u l a r

types - only states w i t h small d i f f e r e n c e s i n a n g u l a r momentum, All (where

123
 I I I I1 Il Il 1 I Il I I I1

AR E I R' - R I ) are shown to share significant coupling. This feature persists

for all values ofR, as shown by the sets of symbols in figures 6.3, and it

also holds for all vibrational transitions. Note that the emphasis of small

AR transitions is independent of any degree of resonance that may occur betwe

the initial and final states of the transition since equation (6.26), from

which these matrix elements are obtained, contains

no reference to the eigen-

energies of the transition.

Nevertheless, resonance enhances the probability for transition. Its

effect, in combination with the preceding small

A R constraint may be

anticipated by examining the relative vibration-rotation eigenenergies

depicted in figure 6.4 for both

H2 and CO. Note that while the transition

vR + v'R' = 0,8 -f 1,0 in para-H2 is nearly resonant,A R = 8 is too large and

the coupling between these states (fig. 6.3(a)) will be very small. Much
5

" " " "CONTINUUM

-
22 - 20 -

4 . 22 - 20 -
18 -
20 -
18 -
20 - 16 -
18 -
I6 - 14 -
- 3
> 18 -
Q)
Y
16 - 14 - 12 -
r.
IO -
5 16 - 14 - l2 -
W 8 -
2 IO - 6-
14 - 12 - 4-
8 - 1 ;
;=
IO- 6 -
12 - 4-
v=3

0
(a) Para-H2

Figure 6.4.- Vibration-rotation eigenenergies for para-H2 CO.

and

124
I

1.0 60 - 50 - 40 -
55 - 45 - 35 -

30 -
.a 40 -
50 - 25 -
35 - 20 -
I5 -
- - 10 -
45 30
25 - .50"
40 - 20 -
v=2
15 -
35 - IO -

30 -
1. p=
v=l
25 -
20 -
.2 15 -
10 -
-5;
180
v=o
0
(b) CO (NOTE: Not all rotational levels are shown).
Figure 6.4- Concluded.
larger A I will be required in
CO to approach resonant transitions while the

restriction to small A R will make the rotational aspect of a vibrational

transition insignificant. From these observations,

we may conclude that, while

transition probabilities are enhanced by vibration-rotation transi-

resonance,

t i o n s w i t h smaZ2 A R wiZ2 dominate the intramoZecuZarenergy transfer process,

regmdZess of resonance!
Finally, we see from figures 6.3 that, although oddA R transitions do

Y = 112, a slightly heteronuclear

not occur in homonuclear molecules where

molecule likeCO (Y = 0.43) will allow oddA R transitions with only moderate

suppression, as indicated by figure

6.3(b). Hence, the selection rule regard-

ing even A R transitions applies strictly to homonuclear molecules.

The foregoing derivation of the molecular equations of motion has expli

itly identified the required trajectory functions. We can now proceed to

evaluate those functions classically in terms of the fundamental collision

parameters.
125
6.1,.
3 Classical Trajectory

of motion are obtained

The classical, two-body, central-force equations

in appendixB as

(6.28)

(6.29)

6.1 and
where the coordinates refer to figure
-V(5) is a spherically symmetric

E, and the correspond-

version of the interaction potential. The total energy,

'u = 42E/l~, are "effective" values averaged over the trajec-

ing initial speed,

tory (as discussed in ch.4 ) .

In this chapter, we shall not include the dynamic influence of the mol

4. To do so in three
cule on the incident particle motion as in chapter

dimensions would require

a great dealof artificial approximation and would

demand extensive comparisons with exact quantum-mechanical solutions for vali-

4.
dation, as in chapter Such an investigation is outside the intent of this

4 as a guide to those colli-

chapter. Instead, we use the results in chapter

sion parameters where the dynamic coupling is unimportant and confine the

examples used here to only those cases.

The form of the interaction potential necessary to determine

a trajectory

is obtained here by spherically averaging the model potential given in equa-

tion (6.2) over all coordinates of the molecule in its initial state. Thus,
-
V(Z) = ( i l v l ((6.30)
&t) li)

where li> denotes the initial state. By use of equation (6.27), the matrix

element abovemay be rewritten in the more workable form:

(6.31)

126
This method of averaging the potential produces
a single trajectory for each

initial state of the molecule and it is independent of the numerous possib

final states. Transition probabilities computed using other methods of aver-

aging (e.g., involving a final state designation) were found to be only negli-

gibly different from those obtained with equation (6.31) when the energy trans-

(6.30) is
fe'rred' inelastically is small compared to the total energy. Equation

an approximation consistent with the adopted classical equations

of.motion

since their accuracy is likewise contingent on the requirement that the energ

traded inelastically remain small.

At this point, we have the sufficient formulation to aobtain

full

(6.4).
numerical solution of equation However, the numerical integration of

a coupled setof differential equations often proceeds with much less labor if

all equations relax at intrinsically similar rates. The selection of step

(t in this case) is then controlled by

intervals in the independent variable

the unanimous behavior of all dependent variables rather than the conflicting

behavior of several dependent-variable subsets. (The amplitudes,

cn(t), and

the trajectory coordinates,

Z(t) and E(t), are conflicting subsets with dissirn-

ilar relaxation rates in this case.) While

a set of equations cannot always be

idealized in such
a manner, the numerical effort is reduced here significantly

by using approximate analytic solutions of the classical trajectory equations

and solving only the,molecular equations of motion numerically.

An analytic solution of the trajectory equations is possible only because

we have adopted an exponential interaction potential.with convenient analytical

properties. In most cases, however, nonexponential potential functions, such

as the Lennard-Jones potential, equation (3.22), can be represented by an
. .

exponential function over the essential regions of interaction with acceptab

127
 accuracy. A d e v e l o p m e n to fa n a l y t i cs o l u t i o n st ot h et r a j e c t o r ye q u a t i o n s is

describedindetail i.nappendix E. The s o l u t i o n s are based on f i r s t - o r d e r

approximations developed by Hansen and Pearsonlo6 and l a t e r extended by

. . S t a l l c o p . l o 7 Here we- o u t l i n e the p r o c e d u r e o n l y b r i e f l y as i t has been

, .adapted i n t h i sa p p l i c a t i o nt oo b t a i nt h ef u n c t i o n sU ( b , t ) and E ( b , t ) .

The f u n c t i o nU ( b , t )d e f i n e d by equation(6.9) may f i r s t b ec o n v e r t e dt o

a more convenientform by n o t i n g t h a t a t c l o s e s ta p p r o a c h t = 0, ? = Xo, and

dE/dt = 0. Equation(6.28) may t h e nb es o l v e df o r v(jio) t oo b t a i n

A e-%o/L V,, -
= E[1 - (b/%0)2] (6.32)
,
Equation(6.9)then becomes

E
- - (-”x X J / L
U(b,t) = - [I - (b/%o)21 e (6.33)
‘ii
When b = 0, w e a l s oh a v et h es o l u t i o n t oe q u a t i o n( 6 . 2 8 )
-
= sech2(g) (6.34)

Hansenand P e a r s o n l o 6 assumed t h a t a s o l u t i o n t o e q u a t i o n ( 6 . 2 8 ) f o r n o n z e r o

‘impact parameters w i l i have a similar form and defined a function, ab(b,t) , so

t h a t ,f o r a l l valuesofb,

e
- (”-x xo)/L =
t)iit/2L]
(b,
sech2
[ab
(6.35)

We show i n appendix E t h a t a n e x p a n s i o n o f b o t h s i d e s o f e q u a t i o n ( 6 . 3 5 )

about t = 0 t h e ng i v e s ,t of i r s t - o r d e r ,

%(b,O) = [l - (b/Xo)2(1 - 2L/Xo)] 1 / 2 (6.36)

Furthermore,exactnumericalsolutionsofequation(6.28) show t h a ta b ( b , t )

v a r i e s s o s l o w l yw i t h t t h a te q u a t i o n( 6 . 3 6 ) may beusedfor all t. Fig-

u r e6 . 5i l l u s t r a t e st h ea c c u r a c yo fe q u a t i o n( 6 . 3 6 )f o rl a r g ei m p a c t param-
I , D

eters where t h e e r r o r i s g r e a t e s t and a t a c o l l i s i o n e n e r g y n e a r t h r e s h o l d .

128
 I .o EXACT
""
EQ. (6.33)
.8

b/L = 14 (b/ji,= 0.995)

.6

.4
.I . .
-2
., .

0 2 4 6 8 1 0 1 2
Et/L

Figure 6 . 5 . - Exact (6.3-

and approximate (eq. 3 ) ) trajectory functions for non-
zero impact parameters; E/AVii = lo+.

A similar figure for 10 times greater would appear almost identical.

energies

Thus, we have the required analytic approximation:

- ~

E
U(b,t) % - [l - (b/~o)2]sech2[a,,(b,0)lt/2L] (6.37)
'i

where ab(b,O) is obtained from equation ( 6 . 3 6 ) and %o is the positive root

of equation ( 6 . 3 2 ) . For small impact parameters where the peak contribution

.X may be approximated by
to vibrational transition cross sections is made,

( 6 . 3 2 ) for b
the analytic expression obtained from equation = 0; namely

.
x
- % 5io(b = 0) = L Zn (6.38)

Figure 6 . 6 indicates the range of b/L where equation( 6 . 3 8 ) may be applied.

. .
i .I

Finally, for very large b/L where b/7co -+ 1, the classical path followsa

6 . 6 indicates, and although equations

straight line, as figure (6.36)

and ( 6 . 3 7 ) are still sufficiently accurate, an alternate and more accurate

approximation is

129
 (6.39)

2o r /
-LINE
I

I1

I I I I I
0 4 8 12 16 20
b/L

Figure 6 . 6 . - Distances of closest approach.

The remaining trajectory function to be determined is

Q(b,t).
- Hansen

and Pearsonlo6 obtain an analytic expression by expanding

Q(b,t)
- in a Taylor

series about t = 0, again where the interaction is greatest, and keeping onl

terms to first order. Thus,

-Q(b,t) = z(b,O) + t(g) t=O
+ ...
( 6 . 2 9 ) , a first order approximation
With the aid of equation i s then

-Q(b,t) %
bii
2t (6.40)
xO

Stallcoplo7 explores the error in neglecting higher-order terms and finds

to increase with A i . . However, the error in cross section is only about

10 percent for A!2 = 4 and appears insensitive to collision energy. We see in

figure 6.3 that the matrix elements and hence cross sections decrease rapid

130
with Ak Ak > 4. Thus, the approximate
and will be of marginal interest for

(6.40) is usedfor its computational simplicity.

function given by equation

6.2 Representations of the Results

(6.4) provide complex probability amplitudes,

The solutions to equation

en(+""), for all states included in vibration-rotation

the set. The final

transition probability from an initial

state I i) .to some other state In)
is then

= l2
In more explicit notation,
we designate the initial state by unprimed quantum

numbers, vam, and denote the probability

(6.41)

m and m', are

However, transitions between individual projection states,

rarely of interest in the analysisa kinetic

of process. A more easily mea-

sured and useful quantity may be referred to vibration-rotation

as the transi-

tion probability, defined as the final probability averaged over all initial

projection states and summed over all final projection states according to

P(E,b) (6.42)
= P(E,b)
v~-+v'a' 2a + m,m'vamtv'a'm'
i : .
Finally, to compare with
a collinear model in which rotational transitions are

nonexistent, we a net vibrational

define transition probability as the total

probability of finding the molecule anywhere in the manifold of rotational

states associated witha designated vibrational state. Sucha probability is

computed simply as the

sum

P(i?,b) = P(E,b) (6.43)

va-tv' a' va-w' a'

131
The net vibrational transition probability
so defined still depends on the

initial rotational state, however, and cannot be compared directly with c

linear predictions. To evaluate the collinear approximation,

we must first

identify the properties of PVR++ that must be obtained to produce similar

cross sections and rate coefficients from either collision model.

The relationof cross sections to transition probabilities has been dis-

cussed in chapter 2 and is known to be

Eo

vR+v'
u(E)
vR+v'
= IT f, P(E,b)b db (6.44)

Equation ( 6 . 4 4 ) poses no difficulty in a three-dimensional model asbut,

chapter 5 demonstrates, its application to the collinear model requires some

additional consideration. Since the impact parameter,

b, is not a collinear

uo, must first be chosen

variable, an effective "hard-sphere" cross section,

by some independent means and the collinear cross section is then defined b

u(B) = uoP(E) (6.45)

WV' w'
The validity of equation ( 6 . 4 5 ) is contingent on the idea that
uo is

invariant with both quantum number and collision energy. Oneof test
the

utility of a collinear model is then to test this contingency by defining

parameter equivalent to uo but obtained from the three-dimensional collision

( 6 . 4 4 ) may be recast into a form defining an

theory. To that end, equation

"equivalent elastic cross section,"u,: by the relation

(6.46)

where

(6.47)

132
and xc is an arbitrary collision radius. Equation ( 6 . 4 7 ) has been written

in a manner that also correlates with other concepts used in the methods

uo.
selecting a hard-sphere cross section, For example, the constant, xc, may

be considered a radius corresponding to the elastic collision radius used t

compute gas-kinetic collision rates.8 The associated elastic cross section is

(6.47).
then the constant term, rxC2, appearing in equation When a Lennard-

is adopted, xc is often equated to the zero-

Jones interaction potential

potential radius and evaluated from viscosity or viral-coefficient

measurements,80

( 6 . 4 7 ) is
The remaining integral term in equation

(6.48)

which may be identified with a "steric factor" often used as a correction f

three-dimensionality with collinear collision models. The steric factor must

be considered invariant in the collinear model, although its magnitude here

-
depends on the valuesof E and the transition quantum numbers. Hence, cases

in which either uoe or S are invariant with both quantum number and colli-

sion energy show possibility as examples where a collinear collision model

applicable. However, the invariance of uoe or S alone is not sufficient to

declare collinear rate-coefficient predictions valid, as shown in the follow-

ing discussion.

4 and 5 , a semiclassically deter-

According to the results in chapters

mined cross section is related

to the thermally averaged rate coefficient, in

the notation of this chapter, by

im+ I
E
'c
k(T)
VR"
=
R'
e
vRv'R' u(E)
VR" R (Z E ~ dE ~ ( 6 . 4 9 )~ ~
133
where
,. ...

If we now assume that transitions for which the steric factor defined by

equation ( 6 . 4 8 ) 'is invariant are those for which

e
vRv' a ' = E
W'
(i.e.,the

contribution of rotational frequencies to the eigenfrequency can be neglected),

then equation (6.49) is well approximated by

(6.50)

To compare with the collinear rate coefficient that presumably represents th

average of all initial rotational states, we introduce a rotational state

population fraction N (T ) that is dependent on a rotational temperature,

vR r
Tr. The net vibrational rate coefficient is then approximately

k(T,Tr)
vrv'
%
-
C u,'
E
e w' irn
[T Nv,(Tr)P(E,O)
VR" 1 (Z + IcWl dZ (6.51)

For cases where =

T Tr, it may be compared directly with a collinear rate

coefficient. The additional conditions to be met before a collinear may

model

be applied are then shown by equation (6.51) to be P that

0) must be rela- (z,
VR"
tively invariantwith quantumnumber, R, and it must vary w i t h i n the same

manner as the coZZinear equivaZent probabiZity.

. .

6.3 Numerical Methods of Solution

(6.4) were
Numerical solutions to the set of differential equations

accomplished using the same algorithm that was applied to the collinear mode

in chapter4 , namely, a fifth-order polynomial extrapolation technique

developed by Bulirsch and Stoer" and provided in FORTRAN by92Gear.

The

method is shown by Hulle t aZ. to be generally advantageous both in

134
 computer expense and reliability (error) over several other established

A typical col-
methods, particularly the frequently used Runge-Kutta methods.

lision event could be computed in this application as 50

with assteps
few

-while-maintaining six-digit accuracy. Most solutions were obtained

with.
. .
100 steps and initialized aatdistance where the interaction potential was
,. .. . .
.. .. . .. , .

of its value at closest approach.

An additional consideration required by the three-dimensional model was

. .
'khe'economic use of computer'storage. The time-independent matrix elements

VVtRlmtvRm,
given by equation (6.26), were computed prior to the numerical

integration and stored in memory. However, their designationa by

sixfold ,

index set suggested by the associated quantum numbers is impractical even

the CDC-7600 computer with its large-core memory. Thus, advantage was taken

of the zeros and symmetry of the matrix elements (see6.1

and an index scheme was

tab1
for examples)

developed that reduced the

r sixfold'matrix
a one- to

dimensional vector with no zeros or duplicate elements. Details of the index

method and its implementation in the computational procedure are described in

appendix
> .
F.

An important conclusion, quickly recognized from early solutions, was

that the number of coupled vibration-rotation states required to a achieve

convergent solution (i.e.,a solution for which the further addition of states

made no change) was too large to be computed

a defensible
in time. For

example, the execution time per step on the CDC-7600 computer was approxi-

mately N2/2 msec, where N is the total number of coupled states.A con-

vergent solution usually requires that at least all energetically accessible

states must be included. Thus, if x denotes the uppermost rotational state,

R and hence (x+1)2

there are' 2R+1 projection states for each orbital state

135
total states from R = 0 to ‘i. Computer time then varies as (I+lp. For
collision energies near vibrational
-E 1 hue
threshold, so that, from fig-

ure 6.4, minimum values

-
are R = 8 for H2 and a = 33 for molecules like
CO.

A corresponding minimum computing time Hefor

collisions is then approximately

5 min - an acceptable value that has allowed numerous studies of vibration-

rotation transition rates in H2. However, for molecules like CO where the

rotational frequency is much less than the vibrational frequency, we could

expect to require more than 18 hr per case! Obviously, to study such mole-

cules, we must seek ways to reduce the required number of coupled states.

greatest reduction will be achieved by any method for decoupling the proje

tion states within a given orbital state and averaging their effects in

advance of the calculation. Several such methods are discussed in the follow-

ing section. Their implementation has been a key factor in reaching the

objectives presented here.

6.4 Effective Hamiltonian and Other Approximations

During the course of this study, three primary methods of approximation

were examined. They are discussed in this sectionanin

order of increasing

utility to this work.

6.4.1 Sudden Rotation/Perturbed Vibration Approximation

In a recent analysis of vibration-rotation coupling in harmonic oscilla-

tions, S t a l l c ~ p ’drew
~ ~ renewed attentionto the concept that rotational and

vibrational motion can be treated in separate limiting approximations. For

example, the rotational period, l/Be, is typically very long compared with th

collision period, T~ = 2Lh. Consequently, the molecule appears rotationally

stationary during the collision period and the induced mixing of rotational

136
states is predict
.ed curately
ac by the "sudden" or "impact" approximation.
56,

The sudden approximation then provides

a closed-form integral description of

the mixed rotational state of the molecule at any time during the encounte

In contrast, the vibrational motion typically undergoes several oscillations

while the incident particle is at close range. Stallcop treats the vibra-

tional motion in the extreme adiabatic limit for which many oscillations m

occur during the interaction period, but that limit is too restrictive for

4 , the broad range of colli-

purposes. Instead, we may recall, from chapter

sion energies in which

a first-order perturbation treatment is successful and

then treat the vibrational motion accordingly. Dynamically, the vibrational

and rotational motions are thus decoupleda and

complete closed-form integral

description of the vibration-rotation transition probability may be obtained.

of the resulting integral equation were

Unfortunately, all series solutions

found to be ill-conditioned and hence not calculable with the significant

digits carried by available computers. Numerous attempts to restructure the

formulation or to evaluate the integral by numerical quadrature were also

unsuccessful for similar reasons. Thus, while the approach is mentioned here

because of its potential significancea means

as of analyzing vibration-

rotation energy transfer, we were forced to abandon it for the present stud

6.4.2 Maximum Coupling Approximation

The broad range of magnitudes covered by the matrix elements,

VVIRlmlvRm,

for the range ofm and m' values suggests that the number of coupled states

of energy transfer. As
may be reduced by including only the dominant paths

figure 6 . 2 indicates, the coupling between vibration-rotation states will

be dominated for large R by the projection states in whichm and m' are

137
 . , . . .
> _

maximum andofthe same s i g n . The "maximum coupling"approximationtherefore

simply excludes a l l states e x c e p t t h o s e c o n t r i b u t i n g . ' i o

%'R' R'VRR and
The number o f c o u p l e d r o t a t i o n a l states i n e a c h v i b r a t i o n a l
1
1
'-R 'VR-R '
, . . .
set i s thenreducedfrom (1+112 t o 2 1 + 1. C a l c u l a t i o n si n c o r p o r a t i n gt h e
,.. .
. .

f o r e g o i n g e x c l u s i o n s are d i s c u s s e d i n t h e f o l l o w i n g s e c t i o n s where they are

compared with the "effective Hamiltonian" approximation described next.

6.4.3 EffectiveHa,miltonian

An approximate method for decoupling and subsequently averaging the con-

tributions of a l l p r o j e c t i o n states o f e a c h o r b i t a l state h a s r e c e n t l y b e e n

developed by Rabitz. 54 Unlikethepreceding two approximations,however,even

therelativerangeof parameters f o r which t h e method i s expectedtobeaccu-

rate h a s n o t b e e n d e f i n e d i n terms o f t h e ' m o l e c u l a r p r o p e r t i e s o r c o l l i s i o n

p a r a m e t e r sn o r is a methodof d e f i n i n g them a p p a r e n t . Hence, f o r t h e p r e s e n t ,

the approximation must simply be tested by c o m p a r i s o n w i t h l i m i t e d e x a c t c a s e s .

I ne f f e c t ,R a b i t zd e t e r m i n e st h e formoftheHamiltonianrequiredto ,

e x a c t l yn u l l i f yt h ec o n t r i b u t i o no fi n d i v i d u a l m and m' states i n t h e m a t r i x

elements. He b e g i n s byassumingan i n t e r a c t i o np o t e n t i a lw i t ht h eg e n e r a l
. .
form, i . .. ,
..? . ,' -
I . ..

I .

and f i n a l l y o b t a i n s t h e e f f e c t i v e m a t r i x e l e m e n t , a n a l o g o u s t o e q u a t i o n ' ( 6 . 5 )

o r( 6 . 2 7 ) , a s

+ .

138
 (6.53)

where VA is an "effective potential" corresponding to equation (6.52).

Equation (6.53) may beconverted to'te& ' corresponding' to the particular

potential, given by equation(6.2), through the useof'equation (6.11). An

equivalence is easily identified as

so that

The resulting "effective" time-independent matrix element

is then

(6.54)

and the complete matrix element, analogous to equation(6.27), is

e
(vlR1IVLlvR) = U(b,t)VvIRlvR (6.55)

The use of equation(6.55) in place of equation(6.27) reduces the totalnu-

ber of coupled rotational states in each vibrational manifold('i+1)2

from to 'i.
Note by comparisonwith equation (6.27) that the inducedphase shift

associated with the exponential argument,(m' - m)z(t), in equation (6.27) is

lost in the effective

Hamiltonian approximation and the remaining formulation

is'independent of
-n(t). We shall see in the dis,cussions to follow, however,

that the rotational energy transfer is dominated by small A2 and hence small

values of m' - m. Thus, even in a complete solution,

'the phase shifts

. . 139
 associatedwithE(t) are subduedandtheaccuracyoftheeffectiveHamiltonian

approximation i s n o t t h r e a t e n e d by t h e i r n e g l e c t .

6.5 AspectsofConvergence

Before applying the preceding three-dimensional model, we f i r s t r e q u i r e a

criterion for choosing a s u f f i c i e n t set o f r o t a t i o n a l a n d v i b r a t i o n a l e i g e n -

states t oe n s u r ec o n v e r g e n c e .E x p e r i e n c ew i t ht h ec o l l i n e a r model(ch. 4)

h a s shown t h a t n e a r t h r e s h o l d o n l y a few states h i g h e r t h a n t h e e n e r g e t i c a l l y

a c c e s s i b l ev i b r a t i o n a l statesare n e c e s s a r yt oo b t a i nc o n v e r g e n c e .T h u s ,f o r
-
g r o u n d - s t a t em o l e c u l e sw i t hE / h o en e a ro rs l i g h t l yg r e a t e rt h a nu n i t y ,o n l y

t h r e eo rf o u rv i b r a t i o n a l s t a t e s are o f t e na d e q u a t e .S i m i l a rc o n c e p t sc a nb e

a p p l i e dt ot h ev i b r a t i o n a l states i n a three-dimensionalmodel. However, t h e

fundamental vibrational frequency of a diatomicmolecule is a l w a y s l a r g e r t h a n

i t s r o t a t i o n a lf r e q u e n c y so t h a t , i n a t h r e e - d i m e n s i o n a lm o d e l ,c o l l i s i o n s

withsufficientenergytoinducevibrationaltransitions
-
( i . e . , E/hw, I 1)

alwayscouplenumerousrotational s t a t e s i n e a c hv i b r a t i o n a lm a n i f o l d . The

b e s t manner o f s e l e c t i n g t h e minimum, and y e t s u f f i c i e n t , number ofcoupled

r o t a t i o n a l s t a t e s f o re a c hv i b r a t i o n a le i g e n e n e r g y is therefore difficult to

d e t e r m i n ei na d v a n c e of a c a l c u l a t i o n . A s e e m i n g l yl o g i c a lf i r s tc h o i c e would

be t o i n c l u d e o n l y t h e e n e r g e t i c a l l y a c c e s s i b l e s t a t e s andexclude a l l others.

For E/hwe = 1, t h i s methodof s e l e c t i o ne n v e l o p s many r o t a t i o n a l s t a t e s i n t h e

initial vibrational manifold and only a few a t t h e n e x t h i g h e r v i b r a t i o n a l

eigenenergy. We s h a l lf i n d , however, t h a t t h i s c r i t e r i o n f o r s e l e c t i o n is not

onlyinadequatetoensureconvergencebutwith a semiclassical formulation i t

a l m o s tc e r t a i n l yg u a r a n t e e s a nonconvergentsolution! The primarypurposeof

thissection is thereforeto examine t h e r e q u i r e m e n t s o f c o n v e r g e n c e i n

140
detail. The reader should be aware at the outset, however, that the results

pertain to our semiclassical model without energy conservation. Their rela-

tionship to the convergence requirements for an energy-conserving collision

model will only be inferred.

We test our ability to obtain convergent solutions for the molecular typ

of interest by choosing the worst numerical case in an example (namely, CO

collisions in which a maximum number of basis states is required) and co

ing the results with those for H2-He collisions, the opposite extreme.

As figure6.4(b) illustrates, a basis set that is convincingly convergent

-
for CO-He collisions at E/hwe2 1 will include an impractical number of

R.
states that extends to large To. deal with such situations,
we must there-

fore first determine the most appropriate method of approximation from sec-

tion 6.4 that will reduce the necessary number of coupled states and that

allows solutions for largeR to be obtained in a practical computing time.

6.5.1 Evaluation of the Projection-State Decoupling Approximations

In keeping with the predominant objective of this chapter to study the

effects of rotational transitions on net vibrational

the transition rates, we

use as a basis for comparison both the probability, PvR-rvl (defined by

eq. (6.43)), and its component, defined by

PvRmtv' = c
R' ,m' PvR" ktm'
(6.56)

Note that the former is averaged over all initial m states while the latter

pertains to a specific initial m state. However, both are summed over all

final R' and m' states in the vibrational manifold, v', and are therefore

both net vibrational transition probabilities.

141
 6 . 4 are methods for decou-
Since the approximations described in section

pling the influence of the projection states on the molecular dynamics and

sequently averaging their effects, the sensitivity of complete solutions to t

quantum number of the initial projection state is an important aspect in

standing of the relationship

of the complete and approximate calculations.

Figure 6.7 shows that, for CO-He collisions,

PvRmv, is relatively insensitive

to the initial value of m, even for large impact parameters where the phase

EFFECTIVE EFFECTIVE
HAMILTONIAN HAMILTONIAN
/

4.

2 bpib--.
- """"" s

- 0 - 0
-3 -2 -I 0 I 2 3 - 3 - 2 -I 0 I 2 3
m m

(a) A = 6 MeV (b) A = 1000 eV

Figure 6.7.- Distribution of net vibrational transition probabilities over the

range of initial projection states for CO(vR= 0,3)-He collisions at
several impact parameters. Only- probabilities for v' = 1 are shown.
Fixed collision parameters are E/hwe= 1.08, L = 0.02 nm. The basis set

.
contained R = 0-8 rotational states in each vibrational manifold and
included all corresponding projection states. Symbols denote results
from: a complete solution,0 0 0 the maximum coupling approxima-
tion. Effective Hamiltonian results appear as a single value.

shift associated with c(b, t) is greatest. This result occurs because no

other dynamical phase interference exists between

m states of the same
-
eigenfrequency w
VR , while S2(b,t) is generally small in the primary region
of interaction (5 = 0 at t = 0 where the interaction is greatest). In view of

the foregoing insensitivityto initial m y vibrational transition probabilities

calculated with an effective Hamiltonian approximate the complete solutions

more accurately than the maximum coupling approximation. Its similar accuracy

in reproducing related net vibrational cross sections is indicated by

142
figure 6.8, where the variations ofpVR-rv'
with impact parameter, calculated

by the two approximations, are compared with complete solutions. Clearly, the

is superior, particularly for the smaller

effective Hamiltonian approximation

interaction scale factor,A, shown in figure6.8(b). (The smaller scale fac-

tor is believed to be more realistic.*') Similar accuracy is obtained for

6.9.
H2-He collisions as shown in figure One should note, however, that the

impressive accuracy of the effective Hamiltonian is aided significantly by

use of the net probability, PvR-rv,,

a basis
as for comparison. Similar com-

parisons for detailed vibration-rotation transitions would not appear as

favorable. Others54,111-113have obtained equivalent results for

a variety of

molecular types.

0 5 IO 15 0 5 IO 15
b/L b/L
(a) A = 6 MeV (b) A = 1000 eV

Figure 6.8.- Variation of net vibrational transition probability with impact

parameter for CO(vR= 0,3)-He collisions using several approximate solu-
tions. Only v' = 1 probabilities are shown. The basis
- set included
R = 0-8 in each vibrational manifold for all cases; = E/hwe
1.08,
L = 0.02 nm. Symbols denote results from a complete solution,0 the
maximum coupling approximation, and a the effective Hamiltonian
approximation.

143
 EFFECTIVE
/HAMILTONIAN

-0
- 2 -I 0 I 2
m

0 2 4 6
b/L

Figure 6.9.- Variation of net vibrational transition probability for

H p (vR = 0,2)-He collisions; v' = 1, E/hwe = 1.1, A =

.,
303 eV, and
L = 0.0273 nm. The basis set included R = 0-10 in both vibrational
manifolds. Symbols denote the results from: a complete solution,
and A , the effective Hamiltonian approximation.

6.5.2 Convergence Requirements for Vibration-Rotation Energy Transfer

The individual vibration-rotation transition probabilities from a com-

plete solution are in figure 6.10 for CO-He collisions at an initial

shown

kinetic energy just above the vibrational threshold. Rotational states from

R = and 1. The
= 0 v
0 to 10 were included equally in vibrational manifolds,

accompanying 484 differential equations and 14,883 dissimilar matrix elements

exceed a practical upper limit for repetitive computation. And yet, compari-

R = 0 to 8 rotational states in each vibra-

son to a similar calculation with

tional manifold shows that convergence in the vibration-rotation probabilitie

is far from realized. However, this result is not surprising

pvR+v' R '
because, while all open channels (energetically accessible states) have been

included in v' = 1, most open channels in v' = 0 are missing (see

fig. 6.4(b) for reference). The interesting result is shown in figure6.11

144
 } z = 0-10
}Z=O-8

Figure 6.10.- Effect of additional rotational states on the vibration-rotation

transition probabilities inCO(vRm = O,O,O)-He collisions. Both cases
were obtained from a complete solution including all projection states
the basis set and vibrational states = v0 , 1. An equal number of rota-
tional states were
- included in each vibrational manifold. Collision
parameters are E/hw, = 1.08, b = 0 . The interaction potentialis
defined by A = 6 MeV, L = 0.02 nm.

145
 I 0-4

'vzm- v1 OPEN
CHANNELS
IN v ' = I
+ CLOSED
CHANNELS
IN V ' = l

-+-
10-5
I
OPEN CLOSED
CHANNELS CHANNELS
IN V ' = I IN VI= I

(b)
I I I I I I I
IO" 5 I I I 10-5 I
I 3 5 7 9 II 13 I 3 5 7 9 II 13 '

NUMBEROFROTATIONALSTATES IN EACH NUMBEROF ROTATIONAL STATES IN EACH

VIBRATIONAL MANIFOLD VIBRATIONALMANIFOLD

CO(vRm
(a) CO(vRm
= O,O,O)-He
(b) = 0,3,3)-He

Figure 6.11.- Convergence of the net vibrational transition probability for CO-He collisions (i.e., the
probability has been summed over all II', m' according to eq. ( 6 . 4 3 ) , but f o r a single
initial m state). A duplicate setof rotational states was included in each vibrational mani-
fold. Only probabilities for v' = 1 are shown. Collision parameters are the same as in
figure 6 . 8 . Symbols denote results from:0 , a complete solution, 0 , the maximum coupling approxi-
mation, A , the effective Hamiltonian approximation.
where we imply from the behavior of for one value of m that, even
PVR"
before all open channels in any vibrational manifold are reached, a converg

in thenet vibrationa2 transition probability,PvR+vl,is obtained! Similar

behavior is found for H,-He collisions, as figure 6.12 indicates. Note that,

in this latter cas.e, calculations including all open channels in both vibra-

tional manifolds were possible and the convergence asymptote is convincingly

unique. Figures 6.11 and 6.12 also include results from the approximate

methods of solution and show them to approach similar asymptotes.

Pvlm-v'

CHANNELS
IN V a l
-
A

--
A A

CLOSED
CHANNELS
IN V ' I
A A A

CHANNELS
IN v . 0
OPEN
-I , CLOSED
-CHANNELS
IN V = O
10-4 I I I
I 3 5 7 9 II 13
NUMBER OF ROTATIONAL STATES IN EACH
VIBRATIONAL MANIFOLD

Figure 6.12.- Convergenceof the net vibrational transition probability for

H2(vRm = 0,4,4)-He collisions. Stipulations and
- symbols are the same
as in figure 6.9. Collisions parameters are E/hwe= 1.5, b = 0 ,
A = 303 eV,L = 0.0273 nm. Note that, in this example, cases are shown
where aZZ open channels are included in both vibrational manifolds.

The uniqueness of the asymptotes obtained in CO-He solutions is not ye

.. .
confirmed, however. In fact, subsequent calculations using the effective

unequal numbers of rotational

Hamiltonian for large but states in each vibra-

tional manifold are shown in figure 6.13 to produce drastically different

results. Note that, even though cases including R = 0 to 40 in v = 0 but

only R = 0 to 10 in v = 2 contain all open channels in both = v0 and 1,

the transition probability is two orders

of magnitude from a final convergence.
147
 EQUAL '1 STATES IN BOTH
VIBRATIONALMANIFOLDS

\ --A" 2 ~ 0 - 4 0IN V=O MANIFOLD

\
\ OPEN (INCLUDES
ALL
\ CHANNELS
IN V = 0)
\
4
\
\
\
\
\
\
\
\
\
.b "
4
0

t
ALL OPEN ALL OPEN

10-5
0
I
IO
VI= I INCLUDED
CHANNELS
20
IN
30 34 40
I
50
I
t
I
V 0 INCLUDED
CHANNELS
I I
IN
I
60
MAXIMUM '1' STATEIN V I = I MANIFOLD

Figure 6.13.- Convergenceof the net vibrational transition probability in

-effective Hamiltonian solutions forCO(vR = 0,3)-He collisions v' = 1,
E/hwe = 1.08, A = 1000 eV, L = 0.02 nm. Cases are represented that
include large but unequal numbers of rotational states in each vibra-
tional manifold. Note that cases are also shown where all open channels
are included in both vibrational manifolds.

A s more rotational states are added to = v1, a final definite convergence is

eventually reached where further additions

of any kind have no effect. Con-

versely, figure 6.13 also demonstrates that cases including a duplicate

of set

rotational states in each vibrational manifold obtain a solution near the

final convergent value with relatively few rotational states. Recall, however,

that the convergence criterion thus implied pertains only to the net vibra-

pvR+v' ' and not the individual vibration-

tional transition probability,

rotation probabilities pvR+v' R ' *

While there is no attempt made here to construct a mathematically

definitive argument showing why a duplicate but nonconvergent set

of rota-

tional states in each vibration manifold produces nearly convergent vibra-

tional transition probabilities, the following conceptual explanation

is

148
o f f e r e d .F i r s t , r e c a l l t h a t eachtime-independentmatrixelement, VV,II,m,vRm,

is a measure of the coupling strength between two v i b r a t i o n - r o t a t i o n states.

The m a t r i x e l e m e n t s are shown i n f i g u r e 6 . 3 t o g e n e r a l l y e m p h a s i z e c o u p l i n g

only between s t a t e s w i t h small d i f f e r e n c e s i n a n g u l a r momentum, r e g a r d l e s s o f

t h ea n g u l a r momentum o f e i t h e r state. Thisemphasis i s p r i m a r i l y a consequence

of the integrated overlap between rotational eigenfunctions of t h e u n d i s t u r b e d

moleculeand it is qualitatively unaffected byany vibrationalchange of

state. A s a r e s u l t ,v i b r a t i o n a lt r a n s i t i o n sa l s oo c c u rp r e d o m i n a n t l yb e t w e e n

states w i t h small d i f f e r e n c e s i n a n g u l a r momentum. We s h a l lr e f e rt os u c h

pairsof states as "companion states" t o i m p l y t h a t t h e i r a n g u l a r momentum i s

similar ( A t i s s m a l l )b u te a c h i s a member of a d i f f e r e n t v i b r a t i o n a l mani-

fold.Thus, i f a r o t a t i o n a l s t a t e has no companion i n t h e b a s i s set ofan

adjacentvibrationalmanifold,directvibrationaltransitions from t h a t r o t a -

t i o n a l s t a t e w i l l beimprobable.

With t h e f o r e g o i n g g e n e r a l p r o p e r t y o f v i b r a t i o n - r o t a t i o n t r a n s i t i o n s i n

mind, w e can now d e s c r i b e i t s e f f e c t on t h e e n e r g y t r a n s f e r p r o c e s s w i t h i n the

averagemoleculeduring a collision. To do s o , we s h a l l a d o p t a p o i n t o f view

compatiblewithourtime-dependent semiclassical modeland refertothe time-

v a r i a n ta m p l i t u d e modulus
1 CvRm ( t ) I a s theinstantaneous''occupation" of

state IvRm). By ''averagemolecule'' w e t h e n mean t h a tt h ep r o g r e s s i o n of s t a t e

occupationsin time provides a t r a c e of theaveragepathofenergy f l u x within

many i d e n t i c a l m o l e c u l e s , a l l e x p e r i e n c i n gi d e n t i c a lc o l l i s i o n s .

Since w e c o n s i d e r c o l l i s i o n e n e r g i e s m a i n l y a b o v e t h e v i b r a t i o n a l t h r e s h -

o l d , many r o t a t i o n a l states are t y p i c a l l ya c c e s s i b l e .E a r l yi nt h ec o l l i s i o n ,

theenergeticallyaccessiblerotational states inthevibrationalmanifold

containing the initial s t a t e become occupied, a l l w i t h similar p r o b a b i l i t i e s .

149
Near closest approach, :vibrational transitions then begin between companion

states and a corresponding occupation distribution develops in the adjacent

vibrational manifolds. However, if the manifold receiving'energy has been

given fewer.rotationa1 states in its basis set, (as it might because a h

manifold would have fewer open channels), then not all rotational instates.

the initial-state manifold have companions. For the energy in those rotational

states to become available for a vibrational transition, it must first return

to a rotational state in the same manifold where a companion exists. Obviousl

of an
such occurrences are the artificial consequence incomplete basis set and

they stress the importance of including at least a duplicate rotational set

each vibrational manifold,(if not a convergent set) to properly reproduce the

transient dynamics during a collision.

We may now ask why a duplicate but incomplete rotational basis set in

each vibrational manifold approximates the convergent solution. Recall that

it does so only for the total occupation of each vibrational manifold, that i

the occupation summed over all rotational states. If all rotational states

have companions as they do in duplicate sets, the most probable paths are

available for vibrational energy transfer from each rotational state consid-

ered and hence no artificial impediment to the energy flow is introduced any

where. However, obtaining the correct net rate of vibrational energy transfer

remains to be questioned. The net rate of energy transfer to all states of a

vibrational manifold may

be written as a sum proportional to the occupation

distribution among its rotational states.At collision energies exceeding

the vibrational threshold, the rotational states are strongly coupled

and the depletionof any rotational state by a vibrational transition

is rapidly restored, thus maintaining the distribution of rotational state

150
occupations in a time scale short compared
to.theencounter period. When

too few rotational- states are.included in the

set!,basis
the occupation

.
distribution is unnaturally constrained and vibrational transitions from'

each rotational state occur, at an rate-but

increased-
'from a fewer .number of

states.., 'Since. all rotational states are closely coupled, no particular

preference is given to vibrational transitions from any of them and the-'net

vibrational. transition rate is only weakly affected,

a s we have observed.

Note, however, that the occupation distribution -of rotational

is stat&

strongly affectedby,thecompleteness of.the'basisset so that convergence

in.the individual vibration-rotation transition rates cannot be e'xpected from

an.incomplete basis set, as we have also observed.

Thus, we have rationalized, in the foregoing explanation, the reasons for

expecting duplicate but nonconvergent sets

of rotational states in each vibra-

tional manifold to closely reproduce the net vibrational dynamics of the mole-

cule given by a convergent set. We shall incorporate this convergence criter-

a11 thein cal-

ion along with use of the effective Hamiltonian approximation

culations of to follow. Conversely, when individual vibration-

pvL+vl
rotation transition probabilities are studied, a duplicate and completely con-

vergent basis set will always be used.

Model

An example of the final rotational state occupations from a convergent

6.14. The distributions in each vibrational

basis set is shown in figure

manifold are plotted on vertically shifted scales to demonstrate their relativ

. .

similarity. However, if we take:the total energy of the system to be the

initial sum of internal energy and relative kinetic energy, then many of
151
 INITIAL STATE V I = 0.3

IO"

10-2 -I

Pvl - v ' t
(VI= 01 (0-3 -I
\ \

10-4
OPEN OPEN
v I ',
- I

CHANNELS CHANNELS
IN V ' = I IN V ' = O

10-5
-4
I I
c

I
i ,
I\ \ i , - I
0 IO 20 30 40 50 60
1'

Figure 6.14.- Vibration-rotation transition probability distributions for

-E/hwe
CO(vll = 0,3)-He collisions from an effective Hamiltonian solution;
= 1.08, b = 0, L = 0.02 nm, A = 1000 eV.

rotational states in thev' = 1 manifold that remain occupied aftCr the col-

lision are energetically inaccessible! (They are closed channels.& Since a

more exact collision model, where total energy is conserved, would leave t

closed channels in all vibrational manifolds completely empty, the failure

our semiclassical model

to comply with such considerations is, of course, a

consequence of the lack

of energy conservation when computing the classical

trajectory, just as 4. We
it was in the collinear model discussed in chapter

4 that, when the

showed in chapter loss of energy conservation had no large

effects on the molecular dynamics, it could be adequately compensated for

(4.14) as
use of the average total energy given in equation
-
ET = E + h(wn + wk)/2 (4.14)

152
However, t h e u s e o f e q u a t i o n ( 4 . 1 4 ) t o c o m p u t e t o t a l e n e r g y makes i t dependent

onthetransitionbeingconsideredand, as a r e s u l t , t h e c o n c e p t o f o p e n a n d

closedchannels becomesambiguous. While t h i sa m b i g u i t yp o s e sn op r a c t i c a l

difficulty, a careful interpretation of the semiclassical r e s u l t s mustbe made

when comparingthem t o energy-conserving predictions - namely, t h e p r o b a b i l i t y

d i s t r i b u t i o n so b t a i n e df o r a s i n g l ev a l u eo f E do n o tc o r r e s p o n dt o a single

total energyorsingleinitialkineticenergyand,consequently,theycannot

be compared d i r e c t l y w i t h a d i s t r i b u t i o n o b t a i n e d f r o m a n e n e r g y - c o n s e r v i n g

c o l l i s i o n model.But, a f t e rt r a n s f o r m i n gt h ed i s t r i b u t i o no fe i t h e rc o l l i s i o n

model i n t o t h e framework o f t h e o t h e r , u s i n g e q u a t i o n ( 4 . 1 4 ) , t h e r e s u l t s

shouldbecomparablejust as they were i n c h a p t e r 4 . The accuracyofthe

three-dimensional semiclassical model i n suchcomparisonsremainstobeproven

and no comparisons are made i n t h i s s t u d y . However,from t h er e s u l t si n

c h a p t e r4 ,t h e r e i s good r e a s o nt oe x p e c tt h a tt h et h r e e - d i m e n s i o n a ls e m i c l a s -

sical model,constrainedtohomonuclearmoleculeswithlightcollisionpartners

and p r o p e r l y i n t e r p r e t e d , s h o u l d g i v e r e a s o n a b l y a c c u r a t e p r e d i c t i o n s .

Final1:r. w e must c o n s i d e r t h e c o n s e q u e n c e s o f t h e ambiguousclosed-

channelconceptonourpreviousconvergencearguments.Whilethe initialdis-

cussionsofconvergenceinfigures6.11to6.13 were keyed t o t h e c o n c e p t o f

openandclosedchannels,they serve mainly as a g u i d e t o i d e n t i f y t h e number

of channelsforwhichconvergence may b ee x p e c t e d .I nt h a tr e g a r d ,t h ec o n c e p t

is as u s e f u l as i t wouldbe i n anenergy-conservingmodel. Recall, however,

thattheprimaryaspectofourconvergencecriterion was toprovide companion

states i n a l l v i b r a t i o n a l m a n i f o l d s t o p r o p e r l y h a n d l e t h e transient dynamics

d u r i n gt h ec o l l i s i o n .T h a tp r i n c i p l ea p p l i e st o a l l c o l l i s i o nm o d e l s ,

153
regardless of their energy-conserving features .-,
or the final rotational-state

occupations.obtained. , . . . . . . .<. .

. ,
.
I , . , .: ... ,

6.7 Three-Dimensional Inelastic Collisions and Their Relation to Collinear

_- . .
. , : -,;

Encounters
. . , ,- -;:! .; . :

The preceding three-dimensional collision model is applied here to eval

.. . . I

ate the validity of collinear models for a variety of molecular types and

initial conditions. However, examples are constrained to collision partners

that can be treated accurately by the semiclassical approximation in the

absence of dynamic coupling between the quantized molecule and the classical

4 in that regard, we consider

trajectory. Guided by the results in chapter

H,, N,,
only helium atom collisions with and CO. The hydrogen molecule is an

example in which the rotational eigenenergies are broadly spaced in compari

with the vibrational energies and the effects of vibration-rotation coupling

are expected to be significant. H, also requires the smallest convergent

basis set since its homonuclear nature only couples rotationalof states
the

same parity (i.e., A L is always even). N2 also requires only states of the

same parity, but its close rotational energy spacing places it in a differe

molecular class where numerous rotational states of high angular momentum

be included. Finally, CO is similar in rotational structure Nto

,, but its
, I .:,

of either parity. Most

heteronuclear nature couples all rotational states

o f th&S&..”
common inert-atom/diatomic-molecule collisions are represented by one

three examples. Excluded cases are those in which reactive atom-exchange

states participate in the energy-transfer process (as in H2-F collisions) an

those in which electronic states participate (as

NO). in

The range of initial rotational states of interest in a practical app

cation is first indicated by considering their equilibrium population

154
distributions. Figure 6.15 illustratessome typical distributions for several

vaiues of the parameter, T/8,, where 8, is a characteristic rotational tem-

perature with representative values2 . 8ofK for CO and 44 K for H p

(er = hBe/sk, where s is a symmetry factor). The results in figure 6.15

11 = 0 to 20 are repre-
suggest that initial rotational states in the range

sentative of most applications. We shall see that the collision dynamics for

larger initial values of11 are easily inferred from the predictions for

E 5 20.

0 IO 20 30 40 50 . .
ORBITALQUANTUMNUMBER, 2

Figure 6.15.- Maxwellian rotational state populations. Numbers at the distri-

bution peaks indicate the corresponding angular momentum quantum numbers.

Finally, we do not attempt to compare collinear and three dimensional

predictions directly by obtaining rate coefficients from each model since to

do so with the three-dimensional model would be too costly. Instead, we shall

155
compare the individual elements contained in the rate coefficient definition

and their variations with the collision parameters, as discussed in sec-

tion 6.2.

6.7.1 H2-He Collisions

Although vibration-rotation energy transfer for Hz-atom collisions

has

been studied extensively in the recent we include

literature,40~54,111,114-118

it here as a contrasting example to the behavior of the heavier molecules

A and L , for all H2-He calcula-

follow. The interaction potential constants,

tions were to resemble the calculated potential of Gordon and Secrest

chosen .84

An indication of the coupling strength between vibration-rotation state

in H2 is given by the matrix elements shown in figure

6.3(a). A s mentioned

A R s 4 provide the primary

previously, the results show that transitions with

path for vibrational energy transfer. The relative levels

of H2 rotational

eigenenergies in each vibrational manifold shown in 6.4(a)

figure then suggest

that transitions from v

= 0 to 1 (for example) will occur with increasing

R -> 10 in v
resonance enhancement from values of = 0, and that the state

vR = 0,16 is in near resonance with v'R'

= 1,14 leaving very little excess

energy to be traded with translation. Such transitions may be considered as

the primary contributors to an apparentV-Rnet

mechanism for energy transfer.

6.16 to 6.18
The calculated transition probabilities shown in figures

confirm all the foregoing expectations. Figure 6.16(a) shows that, when the

initial state is vR = 0,16, transitions occur tov' = 1 predominantly for

AR = 2 downward with large probability and that the occupation of rotationa

states within each vibrational manifold is dispersed, but with less probabil

ity, by A R = 2 transitions in either direction.A sequence of L I E = 2 down-

ward transitions then populates v' = 2, etc., at lower R. Conversely, when

156
 INITIAL INITIAL
STATE STATE

I I I 1

io-' IO"

10-2 10- *

P"1.V' 2'
Pvl -v'l'
, VI= 0

10-3 10-3

I 0-4 CONTINUUM I0-4

LIMITS TO 1'
h
v.210
b
10-5
Ill
0 4 8 12 16 20 24 8
16 12 20 24
FINAL STATE 1' FINALSTATE 1'

(a) H2(vR = 0,16)-He

Figure 6.16.-
- Vibration-rotation transition probability distributions for para-H2(v
= 0)-He collisions
-J at E/hwe = 1.5, b = 0, A = 303 eV, L = 0.0273 nm. Basis set includes R = 0-20 in vibrational
states, v= 0-3. Continbum limits correspond to a dissociation energy of 4.48 eV.
the initial state has small angular momentum, asinshown
figure 6.16(b),

A$ transitions or by
vibrational states are connected either by single large

successive rotational transitions within = v0 that precede any vibrational

change. .The vibrational transition probability is correspondingly lower.

This later example then appears more as a V-T mechanism for energy trans

because of the relatively large amount of translational energy required to

induce a vibrational transition. Intermediate results for other initial rota-

_ . , . _ ..
tional states are summarized in figure 6.17, where the net vibrztional tra

tion probabilities are shown for all initialR below the continuum. (Note

that the molecular dynamics for initial states near the continuum are not

accurately treated because of the neglected continuum interaction, but fig-

ure 6.17 is believed to demonstrate a realistic qualitative behavior.)

We can see from figure 6.17 that the vibrational transition probability

is strongly dependent on the initial rotational state and hence a collinea

model cannot be expectedto realistically predict vibrational transition rates

for Hz. The inapplicabilityof a collinear model to

H2 is further confirmed

by figure 6.18. 6.18 represents the usual

For example, curve (a) in figure

collinear prediction in which the rotational contributions to eigenfrequencie

are entirely excluded. The comparative three-dimensional predictions show

L
that the probability and threshold energy depend strongly on the initial

and both can be significantly different from the collinear results. Further-

more, simple corrections to the collinear model, such as the use

of vibrational

frequencies shifted to match the predominant vibration-rotation states, are

(b) and (c) in figure 6.18 indicate.

not satisfactory as curves

The preceding comparisons were all done for a zero impact parameter, b

we have shown with equation (6.47) that, although collisions bat= 0 make

158
 a

a a
IO"
INITIAL STATE
a
v =o
1 =I6 -THREE-DIMENSIONAL MODEL
$1 - VI
"" COLLINEARMODEL

10-2

INITIAL STATE
V =0
/
1 =2
CONTINUUM
LIMITS TO 1 10-3 .
a .-+
v.210 INCLUDESONLY
v', 1' STATES
/ (0,2) AND (l,4)

INITIALSTATE 1

Figure 6.17.- Effectof initial rotational state Figure 6.18.- A comparison of net vibrational
on the net vibrational transition probabili- transition probabilities for para-Hip(v=O)-He
ties for para-H2(v= 0)-He collisions, collisions from .the three-dimensional and
v' = 1. Collision parameters are the same collinear models; v' = 1. Three-dimensional
as for figure6.16. model includes all states indicated for
figure 6.16.
I

no contribution to the cross section or rate coefficient, the probabilities

b = 0 can be usedas a normalizing factor. Cross sections are then propor-

tional to P(E,O) and the integral of (b/L) P(E,b)/P(E,O) over all b/L. While
vR+v' VR" vR-tv'
adequate discouragement for the use of a collinear theory to model H2 colli-

sions has already been presented, we display the cross-section integrands

6.19 shows the H2

later comparisons with heavier molecule results. Figure

cross-section integrand to depend strongly on initial Q. Figure 6.20 shows

it also to depend on collision energy but with significance only for initia

rotational states where vibrational energy is transferred predominantly thro

V-R transitions (i.e., as in fig. 6.20(b) for vQ = 0,16).

Figure 6.19.- Effectof initial rotational state on the net vibrational cross-
-section integrand for para-H2(v= 0)-He collisions, v' = 1, at
E/hw, = 1.5. Note that the integral of this parameter over all b/L is
(6.46)
proportional to the inelastic cross section according to equations
and (6.47).

160
 3

- 2 -

n
-E / A w ~
I

I
2 4 6 8
b/L 0 2 4 6 8 1 0
b/ L
(a) H2(vR = 0,2)-He, v' = 1 (b) H2(vR = 0,16)-He, v' = 1

Figure 6.20.- Parameters affecting the net vibrational cross-section integrand

for para-H2(v = 0)-He collisions, v' = 1.

From the preceding comparisons, thereno is

difficulty in concluding that

the analysis of vibrational energy in H2, or

transfer any molecule where near-

resonant vibration-rotation transitions with small

AR can occur, requires a

complete three-dimensional treatment including both vibrational and rotational

motions. Furthermore, even though some initial states with small angular

momentum are treated by the collinear mode1,with some resemblance to the thr

dimensional results, extended use of the collinear model to deduce a thermal-

of initial rotation states

rate coefficient enveloping a thermal distribution

is entirely inappropriate.

6.7.2 N2-He Collisions

The calculated collision with

dynamicsN2 of He serve here as the primary

example to illustrate the nature

of vibration-rotation energy transfer in

The N 2
diatomic molecules with closely spaced rotational eigenenergies.
161
molecule provides a considerable computational convenience because, as with

all homonuclear molecules, only alternate rotational states are coupled,

thereby requiring half the basis set demanded by an otherwise similar h

nuclear molecule. Thus, in this section, we study N2-He collisions in detail

and later compare the results with more limited calculations for the hetero-

nuclear CO molecule.

Unlike the H2-He collisions, the interaction potentials for atom colli-

N2 are relatively unknown. The poten-

sions with many-electron molecules like

tial parameters,A and L in equation (6.1), are therefore subject to large

. . .
uncertainties andwe must ensure that any conclusions made concerning the

nature of energy-transfer processes are unaffected by the interaction uncer-

tainties. An indication of the range of uncertainty is obtained by noting the

range of interaction parameters implied in previous comparisons of experimen-

tally determined vibrational rate coefficients with their related collinear

t h e o r i e ~ . ~ ~ For
, ~ ~example,
,~~ L, is typically found
the interaction range,

to be between 0.02 and

0.03 nm with L = 0.02 nm favored for molecules like

87 which yields vibrationally

N2. The analysis of molecular beam experiments,

inelastic cross sections directly, suggest similar values for

L but also

produces values of the interaction magnitudeA. For molecules likeN2,

values are typically nearA = 1000 eV. However, an alternate means of

obtaining A is to compare the exponentially repulsive potential model

(eq. (6.1)) with the repulsive part of Lennard-Jones potentials (eq. (3.22))

implied by early viscosity measurements.

6 ,8 o Magnitudes as large A = 6 MeV
as

are thus obtained. While this later value is not taken seriously nor is our

potential model realistic enough to warrant much detailed interpretation, bo

162
I

of A on the calcu-
values are used here as limits to demonstrate the effects

lated cross sections.

The mechanism of vibrational energy in significantly

transfer is N2 dif-

ferent from that previously shown He.

for The reasons may be generally under-

stood from an examination of the eigenenergies and interaction matrix element

of N2 (illustrated in figs. 6.21 and 6.22, respectively). A well-known fea-

is that their probability is enhanced by

ture of most induced transitions

their degree of resonance. For example, figure 6.17 illustrates the case for

L! = 16 is also the most prob-

H2 in which the most resonant transition from
, . . , ... r. i , ,- - P .-.
able, causing the principal path for energy transfer to V-R through
be transi-

tions. For N,, however, the vibration-rotation eigenenergies shown in

70 -
60 - 50 -
65 - 55 - 45 -
- 40

60 - 50 -
35 -

45 - 30 -
55 -
25 -
40 - 20 -
50 - 15 -
35 - IO -
=3=
45 - ?bo-
v=2
25 -
40 - 20 -
IS -
IO -
35 - "5
a =o'
30 - v= I
25 -
20 -
15
IO
-
-
,.Po
v =o
0'
Figure 6.21.- Vibration-rotation eigenenergies for N2.
(Note: Not all rotational states are shown.)
163
 I

00 1=0
80 1=6
+O 1.40
IO"

\
\
LL = 0.02 nm

\$ \,L=O.O3 nm

I 0-3
\
PARA -Ne

t
2 4 6 0 IO
A1
v, v' = 0, 1.
Figure 6.22.- Time-independent matrix elements for para-N,;
Open symbols are forL = 0.02 nm, solid symbols are for L = 0.03 nm.
A similar plot for ortho-N2 would have no distinguishable differences.

A t , while the
figure 6.21 allow near-resonant transitions only for large

matrix elements for N2(fig. 6.22) suppress large A R transitions, just as

they do inH2 and CO (fig. 6.3). Thus, molecules with a vibration-rotation

spectrum likeN,, characterized by a large value for ue/Be, are always con-

strained to nonresonant V-T transitions with a transition energy approximately

. ..
equal to hue. Consequently, the rotational energy transferred by small AR

transitions is always a small contribution to the total, thus rendering the

vibrational transition rates insensitive to the initial angular momentum.

Figure 6.23 demonstrates that insensitivity for both para- and ortho-N,.

The emphasis of nonresonant V-T transitions and the accompanying rinsen-

sitivity of vibrational transition rates to the initial-state angular moment

164
 10-3 - -

0 PARA N2 (V=O)-He
A ORTHO N2 (V=O)-He

10-5 I I
0 IO 20 30
1

Figure 6.23.- Effect of initial rotational state on the net vibrational trap-
sition probabilities for para-N2(V= 0)-He collisions, v’ = 1. Co1;ision
parameters
are
b = 0, L = 0.02
nm,
E/hwe = 1.1. I ,

I
! ’

are the key factors contributing to a surprising accuracy of the collinear

collision model for predicting transition probabilities N2.

in Vibrational

transition probabilities from both the three-dimensional and collinear model

are compared in figure 6.24. Recall that the interaction potential is charac-

terized only by the range L in the collinear model. Likewise, probabilities

obtained from the three-dimensional model zero

forimpactparameter depend

only on L and hence are independent of A. The three-dimensional predictions

in figure 6.24 therefore represent all values Aof and the only difference

between the two models shown in figure 6.24 is the collision geometry.

The role of A in the three-dimensional model is shown in figure 6.25(a),

where the cross-section integrand is shown as a function of the impact param-

eter. Clearly, A determines the variation of transition probability with

impact parameter and thus determines the relation between

P(b = 0) and the
VR-W’
cross section. In another sense,A determines the equivalent elastic cross
e
section uo (eq. (6.46)), undefined in the collinear model.

165
 I

10-1

pvl - VI

10-2

2 STATE ( V 0.1)

IO-^

Figure 6.24.- A comparison of net vibrational transition probabilities for

para-N2(v = 0)-He collisions from the three-dimensional and collinear
models; v’= 1, b = 0, L = 0.02 nm. Open symbols are three-dimensional
model results. Shaded symbols are equivalent probabilities for
a constant
ae as defined by equation
I (6.46) but set equal to the cross section at
E%we = 0.8, thus simulating the procedure typically applied to collinear
models.

When the interaction potential parameters are fixed, the equivalent

elastic cross section (fig. 6.25(b)) increases slightly with collision energy.

Any variation is contradictory to the assumption made when converting collinea

probabilities to cross sections by of

usea constant hard-sphere cross section,
e
o0 (eq. (6.45)). However, as it turns out, the increase in u approximately
0

equals the increasing difference in P(b=O) between the two collision models
VRSV‘
so that their respective cross sections and rate coefficients are in closer

agreement than figure 6.24 implies. The shaded symbols in figure 6.24 show

166
 .24 -

0 .2 .4 .6 .8 1.0
b/x,

(a) R = 20, E/hwe = 1.1 (b) A = 1000 eV, L = 0.02 nm

Figure 6.25.- Parameters affecting the net vibrational cross-section integrand

for para-N2(v = 0)-He collisions, v' = 1.

the equivalent position of the three-dimensional results corresponding to a

e
constant inelastic cross section obtained using the value ofu from
0
-
E/hwe = 0.8 (i.e., cross sections and rate coefficients from the two models

would. compare graphically as indicated by the collinear model curve and t

shaded symbols).

A further 6.24 pertains to the required

point illustrated in figure

Ne.
vibrational basis set for molecules like The collinear model has been

used as a guide to show that, although the predominant vibrational transitions

are single-quantum
...I
. . , transitions from the ground stakev'to
I 2.
= 1, hi,gher -, I. ,<, . r :

vibrational states participate even at collision energies near threshold. The

three-dimensional model behaves similarly and it was therefore necessary to

, I

include four vibrational manifolds from =v 0 to 3 with R = 0-60 in each

before acceptable convergence was achieved. On the other hand, a collinear,

first-order perturbation calculation of the type described in 4 chapter

gives

results nearly identical to the 11-state collinear model over the:energy

. . ran

included in figure6.24. These comparisons suggest that a first-order

167
 with the
perturbation treatment of the vibrational motion, in conjunction

''sudden approximation" describing the rotational motion, will be a very us

if a
analytical method for dealing with three-dimensional inelastic collisions

workable solution of the resulting integral equation can be found (e.g., rec

sec. 6.4.1).

Another interesting feature of the three-dimensional calculations is the

variation of transition probabilities with impact parameter.

A s shown in

figures 6 . 8 and 6.9, the net vibrational transition probabilities,

pvR",
simply decrease monotonically as the impact parameter becomes so
larger
that

b = 0 impacts always produce the greatest probability of a vibrational tran-

sition. However, the same is not true for all individual vibration-rotation

transitions. The variation of with b is shown in figure 6.26,

pvR+v' R
where some vibration-rotation transitions are seen to be more effectively

induced by nonzero impacts, just as previous classical calculations have

suggested.6 5

STATE 1

0 .I .2 .3 .4 .5
b/xc

-
Figure 6.26.- Vibration-rotation transition probability variations with impact
parameter for para-N2(v= 0)-He collisions atE/hwe=l.l, A=1000 eV,
L = 0.02 nm. Collision radius is xc = 0.3 nm.

168
 Finally, having established the applicability
a collinear
of model for

predicting the rate of vibrational energy transferN p from

initially in the

ground vibrational state, we can now investigate the accuracy of the collin

model in predicting the associated vibrational quantum number dependence of

vibrational energy-transfer rates. The results validate the conclusions of

chapter 5. Figures 6.27 and 6.28 compare both collision models N2

for ini-

tially in the v = 10 vibrational state and show them to be qualitatively

10-1

10-2
21 STATECOLLINEAR

Pvl-v' 5 STATECOLLINEAR

10-3

IO-^

f
10-5 I I I
0 I
-E /bWe 2 3

Figure 6.27.- Comparison of net vibrational transition probabilities for para-

N v = 10)-He collisions from the three-dimensional and collinear models;
vT (= 11, b = 0, L = 0.02 nm. Shaded symbols are equivalent probabilities
e
for a constant u equal to the cross section at E/hwe= 0.5.
0

169
 , . . .2a . . . , _ .

-> .oa
t
c
d
x"
.04

0 .2 .4 .6 .a
b/x,

Figure 6.28.- Parameters affecting the net vibrational cross-section integran

for para-N2(v = 10)-He collisions, v' = 11. Collision parameters are
A = 1000 eV, L = 0.02 nm, xc= 0 . 3 nm.

similar as in the ground-state predictions. When the initial state is vibra-

6.27) to be of sec-
tionally excited, the differences in results are seen (fig.

ondary importance; that is, a larger vibrational basis set is required and

error of the collinear mod.el is slightly greater. The three-dimensional mode

predictions must be compared with the five-state collinear model (dashed lin

in figure6.27 and, clearly, neither set of calculations contains a sufficie

number of vibrational states. Thus, convergent three-dimensional calculations

for excited vibrational states become increasingly impractical, even when the

effective Hamiltonian approximation is incorporated. However, the variation

e
in CJ with collision energy again compensates nicely for the inaccuracy of
0

6.27 indicate. Thus, as

the collinear model as the solid symbols in figure

170
II

before, the collinear model appears to produce an a d e q u a t e d e s c r i p t i o n o f t h e

vibrational quantuwnumber dependence of cross sections and rate c o e f f i c i e n t s

mloi lkeecfuolre s N,. . .

6.7.3 CO-He C o l l i s i o n s '

A comparison of f i g u r e s 6 . 3 ( b ) and6.4(b)for CO w i t h f i g u r e s 6 . 2 1
and 6.22 f o r N2 s u g g e s t s t h a t t h e s t r u c t u r a l p r o p e r t i e s o f CO a r e . v e r y similar

t o N2. The i n t e n t o f t h i s s e c t i o n is t h e r e f o r e t o l o o k m a i n l y f o r e f f e c t s

introduced by t h e h e t e r o n u c l e a r n a t u r e o f CO a s s o c i a t e d w i t h t h e a d d i t i o n a l

coupling of even-andodd-parityrotational states. Generally, no s i g n i f i c a n t

e f f e c t s were found and the conclusions reached for N2 a p p e a r t o a p p l y e q u a l l y

well t o CO. Forexample,figure6.29 i l l u s t r a t e s t h en e tv i b r a t i o n a lt r a n s i -

t i o np r o b a b i l i t yd e p e n d e n c e on R. For small II, t h ev a r i a t i o n so f pVR+V'

are o n l y s l i g h t l y morepronounced i n CO t h a n f o r N,. Figure 6.30shows that

t h e c o l l i n e a r model i s j u s t as a p p l i c a b l e and t h e v i b r a t i o n a l q u a n t u w n u m b e r

Figure 6.29.- E f f e c t o f i n i t i a l r o t a t i o n a l state on the. net vibrational tran-

sition probabilities for CO(v = 0)-He c o l l i s i o n s , v' = 1, a t E/hwe = 1.08,
b = 0, L = 0.02 nm. Basis s e t I n c l u d e s R = 0-60 f o r v i b r a t i o n a l states
v = 0-2.

171
 CO ( V = 5)-He
vl=4

I 3 - 0 MODEL
0 co(vz=O,20)-He,v'=I
A co ( ~ ' 1 5 5 , 2 0 ) - H e , v 1 = 4

I
I T
I
I

I
I 2
I

m w e
3
1
4
I I
5

Figure 6.30.- Comparisons of the net vibrational transition probabilities for

CO-He collisions from the three-dimensional and collinear models. Collin-
ear basis set includes states v= 0-17. Three-dimensional basis set is
the same as shown in figure6.28. Collision parameters are b = 0,
L = 0.02 nm.

6.31 demon-
dependence obtained with it is just as reliable. Finally, figure
e
u
strates that the equivalent elastic cross section, is not profoundly
0,

Np. for
influenced by the collision conditions, any more than it is Thus, we

conclude that when the rotational eigenenergies are closely in

spaced
compari-

son to the vibrational eigenenergies and, hence, no resonant transitions with

small Ak are available, vibrational energy transfer will appearV-Tas a

process regardless of the other molecular properties.

172
 - .2 +vz = O V 3 } E/hUe = 1.08
0 v l = 0.20
k A vz =
->
t vz =

-> 1.7 X: 10-16 cm2

t
C
>
n
1 2-
a
9 I -
I
0 .2 .4 .6 .8
b/x,

Figure 6.31.- Parameters affecting the net vibrational cross-section integrand

A = 1000 eV, L = 0.02 nm, xc = 0.3 nm, v' - v = 1.
for CO-He collisions;

The primary purposeof this chapter is to examine the role of coupled

rotational motion in a diatomic molecule during the collisional ofexchange

vibrational and translational energy.A corollary to that purpose is the

identification of conditions for which a collinear collision model will reali

tically predict the rate

of vibrational energy transfer. We have found that,

although the analysisof rotational coupling is complex, the nature of its

influence on the energy-transfer process is conceptually simple.

The mechanisms of vibrational energy transfer become readily apparent

when one recognizes that the controlling features of vibration-rotation cou-

pling are the predominance of coupling between states with small differences
in angular momentum (i.e., smallA t ) and its interplay with the resonance
enhancement of transition probabilities. Thus, while
we deal with collision

energies that have many rotational states occupied in each vibrational mani-

fold, their occupation occurs primarily through sequential rotational

173
transitions of small A2 during the encounter. Likewise, vibrational mani-

folds are connected primarily by vibration-rotation transitionssmall

with

At. Hence, the predominance of small

Ak transitions is a common feature of

all inelastic mechanisms within the molecule. Furthermore, the range of

Ak

for which rotational states are closely coupled is independent

of the degree

of resonance associated with a transitionit and

is insensitive both to the

interaction potential parameters and

to the inertial properties of the mole-

cule. Thus, the effective range of A R (which we shall refer to as Akma,,

where 0 5 AR ARmax) is similar for all the diatomic molecules and interac-

tion potentials considered here and it is presumably similar for all other

wedl. We have shown (fig. 6 . 3 ) that, typically, ARmx 4 to 6 .

j With small AR transitions as a common characteristic, the different

mechanisms of vibrational energy transfer separate into three natural classe

The molecules belonging to each class are identified by their inertial prop

ties, as specified first and foremost by the ratio of fundamental vibration

and rotational frequencies, we/Be, and, second, by the proximity

of the

initial rotational state to a resonant companion. Given these two identifiers,

we can then anticipate the qualitative nature of vibrational energy transfe

for any diatomic molecule that does not involve electronic motion or reactiv

atom-exchange in the process.

,,,RA
The first class pertains to all molecules in which >>
we/Be

and N2.
regardless of the initial rotational state. Our examples COwere

When the frequency ratio is very large, near-resonant vibration-rotation

transitions of small A R do not exist anywhere in the practical range of

rotational states and any resonant enhancement of largeA2 transitions is

suppressed by the lack of coupling between such states. Consequently, the

174
energy-transfer process is dominated by nonresonantsmall A% transitions in

which the energy is primarily

exchange between vibrational and translational

modes. The initial-state angular momentum then has little influence on the

V-T as
rate of energy transfer and the process is described a
mechanism. Mole-

cules in this class are justifiably treated by a collision

in which
model the

rotational contributionis either averaged or omitted. We found the collinear

model to be surprisingly accurate for this class of molecules.

The second and third classes

of energy transfer pertain to molecules in

wh2ch we/Be is comparable with A!Lmax. Our example was H2. Since we/Be
A E are
is not large, near-resonant vibration-rotation transitions with small

available. The proximity of the initial rotational state to rotational states

capable of near-resonant vibration-rotation transitions then determines the

class of energy transfer in which the molecule belongs.

For example, the

second class may be chosen as those molecules with initial rotational states

remote enough from the near-resonant transitions for their angular to

momentum

be different by an amount greater thanAkmax. Since the rate of energy

transfer through the near-resonant transitions is rapid but proportional to

the occupation of the resonant states, at leastofsome

the resonant states

must first become occupied before the near-resonant transitions canasserve

an effective energy-transfer path. However, the restriction tosmall A%

transitions requires a sequence

of induced rotational transitions to first

take place within the vibrational manifold containing the initial state. Such

a multistep process for successive small rotational energy changes during the
collision is collectively as inefficient as a single-step nonresonant vibra-

tional transition directly from the initial state.

A s a result, the energy-

transfer process will not favor either path and the process must be labele

175
as either V-T
a mechanism in the extreme case orV-R-T
as mechanism
a in which

near-resonant V-R and nonresonant V-T transitions compete.

we/Be
The final class also pertains to molecules with e AR,,, but with

an initial state withinAR,, of a near-resonant vibration-rotation transi-

tion with small A R . Near-resonant vibration-rotation transitions then

immediately dominate the energy-transfer process. Pure

V-R mechanisms of this

type characteristically transfer vibrational energy at rates far exceeding the

previous two classes.

Clearly, these latter two classes involve the rotational motion of the

molecule in a significant manner and a collision model omitting the rotatio

coupling would not distinguish their separate characteristics.

.However,we

have shown that, while the collinear model is not applicable to such molecu

we can at least identify those molecules for which it may be applied by u

simple identifiers.

176
 CHAPTER 7

A REVIEW AND SOME CONSIDERATIONS FORFUTURE STUDY

7.1 Review of the Newfound Aspects of Vibrational Energy Transfer

The primary of this
emphasis study has been directed toward the factors

that influence the collisional exchange rates of vibrational and translational

energy from excited vibrational states of diatomic molecules. In particular,

emphasis has centered on the dependence of energy-transfer rates on initial-

state vibrational quantum number and on the role of coupled rotational tra

tions in the energy-transfer process. As a consequence of the emphasis on

excited vibrational states, two fundamental aspects were included in the col-

lision model that are not often considered, namely, the anharmonicity of the

molecular vibrations and the coupled of multiple

interaction vibrational

states. However, an overriding limitation to the realism of the collision

model is the uncertainty of the interaction potential between collision

partners. Thus, the conclusions of this study pertain mainly to the qualita-

tive natureof vibrational energy transfer with

no attempt madeto predict

absolute rates.

A point made early in this study was that the analysis of a macroscop

nonequilibrium process is most conveniently carried out using simple analytic

formulas to generate the necessary vibrational rate coefficients. One of the

evaluate the several ana-

primary objectives of this study, therefore,to was

lytic approximations in popular use, as they apply to excited state transi-

of the collision dynamics

tions. To that end, a semiclassical description

was adopted because, from previous comparisons, it showed the greatest promis

as a theoretical framework leading to accurate analytical solutions. However,

177
a semiclassical formulation is itself an approximate description of the co

sion dynamics. The first investigative step was therefore to determine the

limitations of the semiclassical approximation when applied to a multistate

anharmonic oscillator initially in an excited state.

A comparative evaluation of the semiclassical approximation was conducte

(ch. 4 ) based on a collinear collision model entirely equivalent to a fully

quantum-mechanical formulation appearing in the literature. Transition

probability predictions were compared for a wide range of anharmonic molecul

types, initial states, and collision parameters. The comparisons also

included heteronuclear molecules. Generally, they were unlike previous com-

parisons in the literature which are typically confined to homonuclear

harmonic oscillators in the ground vibrational state. The results illustrated

some notable and previously unrealized effects

of oscillator anharmonicity on

the semiclassical approximation. For example, when computing the motion of

the incident particle, the usual semiclassical procedure is to consider the

oscillator nuclei as stationary relative

to the molecular mass center.

However, the effects of oscillator compression and recoil are amplified when

the oscillator is anharmonic, and the agreement between semiclassical and

quantal theories is significantly degraded unless the time-dependent average

positions of the oscillator nuclei are introduced into the classical path

determination. In the absence of such coupling, errors in the semiclassical

. . . .

approximation are largest when the incident particle mass is comparable to

larger than the mass of either mclecular nucleus. When the molecule is

heteronuclear, the semiclassical errors can become

so large that anomalous

resonances appear in the transition probability predictions. The anomalous

resonances are strictly a consequence of the anharmonic coupling and do not

178
occur when the oscillator is harmonic. Coupling of the anharmonic oscillator

motion with the classical path removes the resonances and brings the semi-

classical model into acceptable agreement with the exact quantal predictions

These results place new limitations on the use of analytic solutions based

on a semiclassical approximation. For example, the analytic models do not

include the effects of oscillator compression on the classical path and th

should not be applied to heteronuclear anharmonic oscillators like the

hydrogen-halides. For the same reason, the analytic models are also inaccu-

rate when applied to the collision of light homonuclear oscillators with a

heavy incident particle. This latter result is contrary to earlier arguments

based on a concept that the semiclassical approximation should be most accu-

rate for heavy incident particles because their wave packets are more local-

ized and hence their motion corresponds more closely with a classical descrip-

tion. Finally, the limitationsof the semiclassical approximation observed

for oscillators initially in the ground vibrational state no

were befound to

more restrictive for oscillators in an excited state. Thus a semiclassical

collision model should be adequate for studies

of the dependenceof fransition

rates on the initial vibrational quantum number.

With the semiclassical approximation validated and its limitations

understood, the factors influencing the dependence of vibrational rate coeffi-

5). (ch.
cients on the initial state quantum number were investigated next

Again, a collinear model was used, this time because it corresponds to the

collision geometry adopted in all the analytic solutions to be tested. Com-

parisons of the several analytic solutions available from the literature with

multistate numerical solutions for anharmonic oscillators in excited states

179
 . . ... .

in applications
showed that the most accurate analytical description where

is a first-order perturbation treatment of anhar-

the accuracy is important

in greatest popular use was

monic oscillators. Conversely, the approximation

found to give the poorest results for highly excited states. The influence

of multiple-quantum transitions on the vibrational relaxation process from

Two- and three-quantum transitions

highly excited states was also examined.

from highly excited states were found

be generally
to unimportant at kinetic

temperatures less than the characteristic vibrational temperature

of the

oscillator (defined as hwe/k). Since vibrational relaxation is usually

superceded by other kinetic mechanisms at higher temperatures, the usual

assumption that single-quantum transitions prevail is adequate for the range

of initial vibrational states typically considered.

The remaining question pertains to the role of coupled rotational tr

tions in the transfer of vibrational energy and their impact on the pre

conclusions obtained with a collinear collision model.

A three-dimensional

6 ) that allows an arbitrary number

collision model was developed (ch. of

coupled rotational states to be included in the arbitrary set of vibrati

manifolds. However, the collision calculations only confirm what is apparent

(in retrospect) from the matrix elements associated with all diatomic

vibration-rotation states: namely, that the two controlling factors of rota

tional coupling are (a) a restriction to vibration-rotation transitions with

small changes in angular momentum (b)

andthe interaction of that restriction

with the rate enhancement given to near-resonant transitions. Based on these

general features, one can classify the mechanisms of vibrational energy

transfer between a diatomic molecule and a structureless particle into thr

distinct types: vibration-translation (V-T), vibration-rotation-translation

180
(V-R-T), and vibration-rotation (V-R). The molecules belonging to each type

are easily identified, first and foremost by their ratio of fundamental vib

tional and rotational frequencies, ue/Be, and, second, by the proximity of

their initial rotational state to a near-resonant transition invoking a smal

A result particularly important to the analyst of

change in angular momentum.

macroscopic kinetics is the finding that molecules belonging to the class

>> 1) are accurately

dominated by V-T transitions (i.e., those where ue/Be

treated by a collinear collision model that may be reduced to yield analyti

solutions.

As a consequence of this study, we reach the broad conclusion that the

collisional exchange rates of vibrational and translational energy can be

accurately estimatedfor diatomic molecules in excited vibrational states

using a simple analytic semiclassical model if the following conditions are

met:

(a) The fundamental vibrational frequency

of the molecule is larger than

of magnitude.
its rotational frequency by several orders

(b) The molecule is homonuclear or only slightly heteronuclear.

mass is less than either nuclear

(c) The incident particle mass of the

molecule.

(d) The interaction potential is accurately modeled in the region of

closest approach.

(e) A theoretical model is used that includes oscillator anharmonicity

in its primary formulation. The first-order perturbation treatment of Morse

oscillators appears to be the most satisfactory choice.

While the preceding conditions are numerous, they only exclude light or

He and the hydrogen-halides, or collision

heteronuclear molecules, like

181
 partners heavier than Argon. Hence the limitationsa well-chosen
of analytic

model are not severe.

7.2 Considerations
Study Future for . .

Long before this

study.wasconceived, many investigators were of
aware

the need for more detailed descriptions

o f the interaction potentials between

simple diatomic molecules and atoms or ions. The computational and experi-

mental determination of such potentials continues to be . . an.activity

of.fore-

most importance if quantitatively accurate predictions of vibrational and

rotational energy-transfer -rates are to be achieved. Clearly, many other

related collision phenomena such atom exchange reaction rates, ion and a

recombination rates, and collisional radiative line broadening also await

same potentials. However, the theoretical and experimental methods for deter-

mining interaction potentials are usually somewhat from

remote
the physics of

inelastic collisions discussed here. We only acknowledge their importance

to future studies of this type. In fact, with exact quantum-mechanical calcu-

lations of inelastic collisions now effectively

a routine numerical exercise,

much of the new work on vibrational and rotational energy transfer is ba

on the availability of improved potentials.

Nevertheless, there are new practical applications, particularly those

associated with lasers, that require further study into several untouched

aspects of vibrational energy transfer. For example, we

iflimit our interest

just to the exchange

of vibrational and translational energy and exclude the

multitude of other vibrational exchange mechanisms such as vibrational ener

transfer between two oscillators or the interactions between vibrational an

electronic states,we are still left with the following considerations:

182
 ' (a) The absence of satisfactory experimental determinations<of the, depen-

dence of vibrational rate coefficients on initial-state quantumnumber was

indicated in chapter5. Clearly, such measurements will be difficult, but

. .

recent improved techniques for selective excitation of upper states using

. - , .. . . . .

tunable lasers and multiphoton absorption offer possibilities for new

.
" . .. . . , ,

approaches.
. .

(b) The use of a semiclassical approximation and the deletion of long-

. . . !

range forces from the interaction have made the collision models of this
. .
study inappropriate for predicting low-temperature rate coefficients. we
Yet
' /

have shown that the rate predictions for transitions from highly excited

vibrational states are most sensitive to the collision parameters at low

temperatures. Several infrared lasers of great practical importance operate

at such conditions. Thus, rate predictions using a fully quantum-mechanical

model and a more complete description of the long-range interactions

be would

extremely useful for the analysis of such lasers. The same collision models

would also advance the study of heteronuclear molecules at all conditions

since, for those molecules, the semiclassical approximation is generally

inappropriate.

(c) Molecules like

H2 are shown to transfer vibrational energy with high
. I , . . I : ( ! . I T.., 3 . : 1 : , * ! v > . . . L d . ..,,
probability from rotational states near the continuum. Clearly, more realis-

tic predictions of such energy-transfer rates should include interactions with

the continuum. Furthermore, a collision model including continuum states

would allow further study into the nature of vibration-dissociation coupling

vibrational states.
. . ,

183
 The foregoing considerations have come mind
to during the course of this

study as a result of the particular topics investigated. However, recent

excitation of vibrational states

innovative techniques using the selective

in such applications
as laser isotope separation, photoenhancement
of chem-

ical reactions, and fluorescence enhancement have brought importance to many

other aspects of vibrational energy transfer not considered here.

Ames Research Center

National Aeronautics and SpaceAdministration
Moffett Field, Calif.94035, March 4 , 1976

184
 APPENDIX A

NOTATION

The following catalog

of symbols includes only those used repeatedly.

All symbols are defined locally in the text. Equations and figures cited
locate explicit definitions and usage.

a Morse intramolecular potential range, equation (3.3)

trajectory coefficient for nonzero impacts, equation (6.36)

ab
A interaction potential magnitude, equation (3.18)

b impact parameter, figure 6.1

b' ,bv Morse oscillator wave-function constants, equation (3.10)

molecular rotational frequency constant

Be
C wave-function amplitude in basis state
n
n
D Lennard-Jones interaction potential well depth, equation
(3.22)

Morse intramolecular potential well depth, equation (3.3)

E relative kinetic energy a

incenter-of-mass reference frame
-E average relative kinetic energy

oscillator energy in eigenstate v

total energy of
a colliding system in
a center-of-mass reference
ET
frame, equation (4.15)
h h/21~,where h is the Planck constant

i, (Y 1 modifiedqspherical Bessel function, equation (3.31)

k Boltzmann's constant

k' oscillator anharmonicity constant, equation (3.9)

km,nsk- rate coefficient for transitions from quantum state

rn to n

185
 -". -. . . .---.--.. - ... .
I., .. "111 I I ... ...."."
I
"

a,a' angular-momentum orbital quantum numbers . ' "

..
,.
L I
interaction potential range parameter, equation. (3.18)
b
Lv(Y1 Laquerre polynomial, equation(C.2) '

m,m' angular-momentum projection

quantum : numbers

m m' -m

mi mass of nucleous i
I , . . 1 .
. .
- .>

rotational matrix element coupling term, equation (6.22)

oscillator radial wave-function normalization factor,

NV
:i
equation (3.6)

Legendre polynomial in the variable

y , I

transition probability between statesm and n

, .
final transition probability from state v'R'm' to vRm

net vibration-rotation transition probability averaged over

all initial m states and skmed over all m' stated, "

equation (6.42)
1

net vibrational transition probability averaged over all

pVa3v'
initial m states and summed over all11' and m' states

in manifoldv' , equation (6.43)

r oscillator internuclear separation distance

r oscillator equilibrium internuclear separation distanee

e *i

(n) elementary radial overlap integral, equation (6.19)

rw'
oscillator radial wave function for eigenstate v,

equation (3.6)

radial matrix element, equation (6.16)

time measured from the instant of closest approach

186
T kinetic temperature
-
U average relative collision speed in
center-of-mass
a

reference frame

U interaction-potential spherically symmetric term,

. . equation (6.9)

v,v' vibrational quantum number

V,V' interaction potential between colliding nuclei

v (6.30)
spherically averaged interaction potential, equation

intramolecular potential

time-dependent interation matrix element (overlap integral)

for states m and n

time-independent matrix element for states v'R'm" and

vRm, equation (6.26)

"ef f ective-Hamiltonian" matrix element, equation

(6.55)

separation distance between colliding nuclei, figure

3.4

"hard sphere" collision radius

mass-center separation distance between collision partners,

figure 3.4

mass-center separation distanceat closest approach

. .
, .. .. ,,:: , . - I ...
X anharmonic second-order frequency coefficient, equation(3.1)
e
spherical harmonic function

z (3.7)
oscillator-internuclear separation parameter, equation

Y mlecular miss ratio,

figure 3.4
B molecular orientation angle,
figure 3.4

Aa Ia"a I
 gamma function of argument y

incomplete gamma function

6.1
spherical polar coordinate angles, figure

II pair
reduced mass of the collision

reduced mass of the molecule

Lennard-Jones zero potential radius, figure 3.3

(5.4)
"hard-sphere" constant cross sections, equation

equivalent hard-sphere cross section computed from the

three-dimensional collision model, equation (6.47)

(5 total cross section for transitions from state mn to

mtn
T (1.1)
vibrational relaxation time constant, equation

mean collision-interaction time

oscillator steady-state wave function

Y perturbed oscillator time-dependent wave function

w circular frequencyof eigenstate m

m
w fundamental oscillator frequency, equation (3.1)
e
w w -w
mn m n
-
s2 trajectory azimuthal angle, figure 6.1

188
 APPENDIX B

GENERAL FORMULATION OF THE SEMICLASSICALCOLLISION THEORY

The semiclassical procedure developed here i s assembled from the contents

o ft y p i c a lt e x t b o o k sd e s c r i b i n g classical andquantummechanics.Forexample,

t h e classical equations of motion are d e r i v e d f r o m f i r s t p r i n c i p l e s i n H.

Goldstein, CZassicaZ Mechanics, Addison-Wesley(1950),chapter 3 , a n dt h e

quantum-mechanicalmethods are d i s c u s s e d i n E. Merzbacher, QuantumMechanics,

JohnWiley(1970),chapter 18. B o t ha s p e c t s are i n c l u d e dh e r et op r o v i d e a

unified description of the complete theory and to identify explicitly the

notation and assumptions associated with the collision model.

The f o r m u l a t i o n t o f o l l o w i s basedon a center-of-massreferenceframe

i n which p, and p denotethereduced mass o ft h et a r g e tm o l e c u l e and t h e

c o m p l e t ec o l l i s i o ns y s t e m ,r e s p e c t i v e l y . The i n c i d e n tp a r t i c l e is limited

here to a structureless point mass whose motion i s p i c t u r e d c l a s s i c a l l y .

The t a r g e t m o l e c u l e is capable of intranuclear motion and i t s dynamic response

t o a time-dependentdisturbanceinduced by t h e i n c i d e n t p a r t i c l e is described

quantummechanically.Themotionsofbothcollisionpartners are coupled

throughaninteractionpotentialthatdependsonthe r e l a t i v e s e p a r a t i o n of

a l l n u c l e ii nt h es y s t e m .F o rt h e s ep u r p o s e s ,t h ep o t e n t i a l is represented
-f
h e r eo n l y by a na r b i t r a r yf u n c t i o n V(5,;) when
q s p e c i f i e st h em o l e c u l a r
3
c o o r d i n a t e si nc o n f i g u r a t i o ns p a c e and R l o c a t e st h ei n c i d e n tp a r t i c l e

p o s i t i o n r e l a t i v e t ot h em o l e c u l a r mass c e n t e r . The r e m a i n i n gd i s c u s s i o n may

then be divided into a section describing the classical m o t i o n o f t h e i n c i d e n t

p a r t i c l e and a s e c t i o n d e t a i l i n g t h e quantum-mechanicalformulationforthe

molecular dynamics.

189
 B.1 Classical T r a j e c t o r y

I n most semiclassical c o l l i s i o n t h e o r i e s , t h e classical p a t h is d e t e r -

minedfrom j u s t a s p h e r i c a l l y symmetric average of t h e i n t e r a c t i o n p o t e n t i a l

c e n t e r e do nt h et a r g e t mass c e n t e r . T h i s a p p r o a c h r e d u c e s t h e e n c o u n t e r t o a

simple two-body central-forceproblemand,moreimportantly, i t avoidsmost

of the difficulties arising otherwise from a need t o d e f i n e t h e m o l e c u l a r

i
coordinate q, c o n t a i n e d i n t h e i n t e r a c t i o n p o t e n t i a l , i n classical terms.
The s p h e r i c a l l y symmetric a v e r a g e p o t e n t i a l , v, may be obtained byquantum

mechanically averaging the potential over a l l molecular coordinates in a

manner suggested by

wheremolecular states Ij ) and In) may be i n i t i a l states o r some combina-

tionofinitialandfinal states. I n many cases, t h e methodofaveraginghas

little influence on the final results.

Given a c e n t r a l p o t e n t i a l , t h e t r a j e c t o r y r e m a i n s i n a single plane

d e s c r i b e d by two c o o r d i n a t e s as shown i n f i g u r e B . l . The p o t e n t i a l may t h e n

bedenoted as V(V$(),) a n dt h et r a j e c t o r y i s c o n v e n i e n t l yd e s c r i b e d

by a Lagrangiandevelopment of theequationsofmotion. As a r e s u l t , t h e

c o n s e r v a t i o no ft o t a le n e r g y , E, l e a d s t o

and t h e c o n s e r v a t i o n o f a n g u l a r momentum, L, requiresthat

190
 \"f

/c LINE OF SYMMETRY AT
CLOSEST APPROACH

/-\MOLECULE MASS CENTER

Figure B.1.- Classical pathin a center-of-mass reference frame

for a two-body, central force interaction.

The initial conditions are defined by the initial speed, ui, and the impact
parameter, b. At t = -m, we then have E = (1/2)vu: and L = pbui. However,

before introducing the initial conditions, we must recognize that no account

has been taken of the energy or angular momentum traded inelastically with

the target. This inconsistency is the origin of the lack of conservation in

a semiclassical theory. While, in principle,a further approximation could

be invented for keeping the system conservative, the usual method has been

E and L
to adopt an equally approximate approach in which are simply

interpreted as "effective" constants of the motion averaged over the trajec-

tory. b and b' ,

In this formulation,we shall consider the impact parameters

# u in a fully
shown in figure B . l to be identical but acknowledge that u
f i
"

conservative system. We then define an average speed,

u = u(ui,uf) and average
-
energy E = 1/2 pti2, where the method of averaging is determined by that giving

the best results. With these interpretations, the equations of motion that
+ +
of the coordinate R = R (Z,E)
determine the time dependence in the inter-

action potential are obtained from equation (B1) and (B2) as

191
B.2 Quantum-MechanicalMolecularMotion

The molecular motion i s d r i v e n by the complete interaction potential,

++
V(q,R). To emphasizethe t i m e dependence,however, w e u s et h ee q u i v a l e n t

notation V(4,S)
V(5,t). The Hamiltonian
describing
the
molecular
motion

i s then

Jc(3,t) = Jco(d) + V ( 5 , t )
-+
whereXo(q) i s t h es t a t i o n a r y - s t a t eH a m i l t o n i a nc o n t a i n i n gt h ei n t r a -

m o l e c u l ap
r otential Vo a c c o r d i n gt o

T h i sd e f i n i t i o n of Jc(<,t), i n w h i c h t h e i n c i d e n t p a r t i c l e m o t i o n i s only
-f
implied by t h e time dependence of V ( q , t ) , i s t h ee s s e n c e of t h e s e m i c l a s s i c a l
-f
approximation.Otherwise,Jc(q,t)wouldcontain a momentum o p e r a t o rr e l a t e d

totheincidentparticle.

IntheSchrodingerpicture,theequation ofmotion is

For t -f t-, t h em o l e c u l e i s undisturbedand JC = KO, g i v i n g a s t a t i o n a r y -

s t a t e s o l u t i o n of t h e form

192
where the probability amplitudes,
c(
nO) and c(O)k are constant in time.

(B7) represents bound states ofKO with quantum

The first term in equation

numbers n and satisfying

= '
n n

.X with
The second term accounts for any continuum states allowed by

energy Ek and momentum hz. While continuum states may exist,

we justify

their neglect by arguing that they will never participate in the dynamics

of the molecule for the conditions of interest here. Consequently,

we shall

always choose total energies (internal plus kinetic) well below the level

where any continuum states are energetically accessible. With that

stipulation, the bound-state

eigenfunctions, providea natural and
n' 9
(B6).
complete basis set in which to expand the solution to equation Thus,

we can write the time-dependent wave function as

The probability amplitudes,cn(t), are analogous to c(O), but are now time
n
dependent. The probability of occupation in staten at any time during

the encounter is I
<Qn,:(Y t)> = I cn(t) I '. Since all that
we desire are the

occupation probabilities, a description of the c (t) terms provides an

n
(B6) may be transformed into
adequate solution to the problem. Equation a
where the bracket notation refers to

+
i n t e g r a t e do v e r all q space.

To solve equation (B9), the molecule is c o n s i d e r e d t o b e i n i t i a l l y i n a

p u r ee i g e n s t a t e I i ), t h u s c r e a t i n g t h e i n i t i a l c o n d i t i o n

for all n.
The i n i t i a l phaseof c,(--) i s unimportantand is chosen

arbitrarilysince w e are i n t e r e s t e d o n l y i n I c n ( t ) I 2. The f i n a l s t a t e of

themolecule at t * sdo t h e nd e t e r m i n e st h et r a n s i t i o np r o b a b i l i t i e s

r e s u l t i n g from t h e c o l l i s i o n . For t r a n s i t i o n s t o state I j ) , t h ep r o b a b i l i t y

is

A t this point, note the role of various terms i n e q u a t i o n (B9) and how

t h e yc o n t r i b u t et ot h et r a n s i t i o np r o b a b i l i t y . The matrix element,

( jIV(<,t)In), is a c o u p l i n g f a c t o r t h a t c o n n e c t s states I j) and In). It

containstheprimaryquantalpropertiesofthetransition and i t i n t r o d u c e s

t h ea p p r o p r i a t es e l e c t i o nr u l e s ,i f any e x i s t . However, w h i l e s e l e c t i o n r u l e s

w i l l controlindividualmatrixelements,thecouplingof more t h a n two states

in the molecular dynamics can allow alternate routes for the molecule to

r e a c h a s e l e c t e df i n a l state. Thus, e n e r g e t i cc o l l i s i o n si n v o l v i n g numerous

i n t e r m e d i a t e states w i l l n o t a l w a y s d i s p l a y t h e s e l e c t i o n p r o p e r t i e s a p p e a r -

i n g i n low-energy c o l l i s i o n s whereonly two s t a t e s p a r t i c i p a t e i n a t r a n s i -

t ion.

194
 Resonance ina transition plays no direct role in determining the matrix

element properties. Thus, the matrix-element properties will prevail regard-

additiotzQZ
less of the degree of resonance. However, resonance will have an

effect on the transition probability by of

waythe phase term in equation(B9).

Clearly, a resonant transition (in which

w j = un) will not be degraded by

phase interference during the collision and will achieve the maximum proba-

bility determined by the matrix element. Conversely, Ias

uj - wn I
increases, phase interference can add an oscillatory structure to the final'

transition probability that varies with the collisional parameters.

of solving equation (B9) are made simpler if the

The practical aspects

(B10) may be
time-dependent aspectof the matrix elements defined by equation

factored according to

Then the time-independent elements Vjn, which contain all the quantum-

mechanical selection properties and often require considerable numerical labor,

can be computed in advance

of the time-dependent solution. The function U(t)

is obtained from the classical trajectory and applies to the entire

of set
..
. I . . .
equations (B9) for all quantum states.

(B9) is to adopt the

Another practical aspect in solving equation

so-called "close-coupling" approximation in which not all eigenstates in the

complete set are included., Guided by trial solutions, only those states

of interest are retained

contributing to the dynamics of selected states in

the coupled set of equations

(B9). Usually, many states that are energetically

inaccessible froma classical point of view may be neglected, although

195
 experience has shown t h a t i n a c c e s s i b l e states w i t h e i g e n e n e r g i e s c l o s e t o a

state of interest contribute t o thetransientdynamicsduringthe co~lisio~

eventhoughthey are unoccupiedafterward.

Finally, a necessary criterion that w i l l b e s a t i s f i e d a t any time, i f

t h en u m e r i c a ls o l u t i o n of e q u a t i o n s (B9) p r o c e e d s a c c u r a t e l y , is theclosure

relationconservingprobability,that is,

Hence, e q u a t i o n ( B 1 2 ) may beused as one t e s t f o r r e g u l a t i n g t h e n u m e r i c a l

stepsize,although,inpractice, i t seldombecomes a limitingfactor.

B.3 First-OrderPerturbationTheory

When t h e k i n e t i c e n e r g y i s very l o w , t h e o c c u p a t i o n o f a l l states o t h e r

t h a nt h ei n i t i a l s t a t e remainvery small. Thus, i f li) d e n o t e st h ei n i t i a l

s t a t e , we canassume I ci(t) 1 1 and Icn(t) I << 1 f o r a l l times and a l l

n # i. To o b t a i n t h e e q u i v a l e n t o f a f i r s t - o r d e rp e r t u r b a t i o nt h e o r y in

thesecircumstances, w e must make t h e f u r t h e r s t i p u l a t i o n t h a t o n l y two

states i n t e r a c t ,w i t ho n eo f them t h e i n i t i a l state. T h i ss u g g e s t st h a tt h e

eigenenergyofthesecond s t a t e i s remotefrom a l l o t h e r s and l i e s a d j a c e n t

t ot h e i n i t i a l - s t a t e eigenenergy. I f , f o rs i m p l i f i c a t i o no fn o t a t i o n , we.

denote

e q u a t i o n (B9) c a n t h e n b e w r i t t e n :

196
The n e g l e c t of cn i n e q u a t i o n (B14) c o n s t i t u t e s t h e p e r t u r b a t i o n a p p r o x i m a t i o n

a n dl e a d st o a v i o l a t i o no fc l o s u r e as givenbyequation(B12). The set of

e q u a t i o n s (B14) and (B15) a r e t h e r e f o r e n o t e x a c t l y e q u i v a l e n t t o a two-state

d e s c r i p t i o nu s i n ge q u a t i o n s( B 9 ) .

A solutionofequation (B14) i s

c ( t ) = exp
i
[-: f -m
Vii(T)d-c
1
t h u sf i x i n gt h eo c c u p a t i o n Ici(t) I = 1 for a l l t. Equation (B16) i s used

t o s u g g e s t h ef o r mo fc n ( t ) by w r i t i n p

whereIcn(t) l2 = Ibn(t) 12. Thus, w e may s o l v ef o rb n ( t ) .E q u a t i o n (B15) ,

i n terms o fb n ( t ) ,t a k e s on theconvenientform

By d e f i n i n g a phasefrequency rni = w
n
- w
i
+ (VAn - V ! . ) / h ,t h et r a n s i t i o n
11

p r o b a b i l i t y i s t h e no b t a i n e di ns i m p l ef o r m as

197
198
 APPENDIX C

RADIAL MATRIXELEMENT INTEGRAL

The r a d i a l matrix element (J) is e x p r e s s e d i n e q u a t i o n

Rw, (6.18) as a

series e x p a n s i o nc o n t a i n i n gt h ei n t e g r a l sr ( n )w h e r e ,a c c o r d i n g t o equa-
W'
t i o n( 6 . 1 9 ) ,

(6.19)

The i n t e g r a l r (n) m u s t b ee v a l u a t e df o r a s u f f i c i e n tr a n g e of n to r e a c h
W'
convergence i n (J). We t h e r e f o r es e e ka na n a l y t i cs o l u t i o nt o equa-
RW'

t i o n( 6 . 1 9 )f o ra r b i t r a r y n t h a t w i l l a l l o wr a p i dc a l c u l a t i o n s of t h e

numerous m a t r i x e l e m e n t s r e q u i r e d f o r a typical basis set of v i b r a t i o n a l

states.

The f i r s t s t e p i n e v a l u a t i n g e q u a t i o n ( 6 . 1 9 ) is t o express i t i n

e x p l i c i at l g e b r a i c terms. To t h aet n d , w e recall t h a t (r) and 6i,(r)

are Morse o s c i l l a t o r r a d i a l wave f u n c t i o n s d e s c r i b e d i n c h a p t e r 3. Morse72

shows t h a t , i n t h e a b s e n c e o f r o t a t i o n a l c e n t r i f u g a l f o r c e s , t h e wave

f u n c t i o n may b e w r i t t e n :

where

z = k ' ea(r-re)

bV
=k' - 2 ~ 1-

Nv
= [abvr(v + l)/r(k' - v)] 1/2

199
and v is an integer denoting the vibrational
eigenstate quantum number.

m e function L>(z) is a Laguerre polynomial defined as73

where

and T(y)
m! (v
(-1) - r(k'
- m) ! r(k' - 2v + m)
- V)

is a gamma function. By comparing the eigenenergies associated

with R (r) with the spectroscopic term expression:

V

E /h =
V
W
,
(V + 1/2) - uexe(v + 1/2)2
k'
Morse shows that the parameter is then a measure of the oscillator

anharmonicity and related to the spectroscopic parameters by

k' = ue/uexe (C3)

Substitution of the radial wave-function expression, equation

(Cl), into

z
equation (6.19) leads toa transformed integral over the variable

according to

I . . . ,

where is a Kronecker delta and the new terms are defined by

bW'

Nwl = NvNvr/a

- v(k' - -
2~ 1) (k' -2 ~ '- l)V!V' !
r ( k ' - V) r ( k ' v')- (C5)

and

A = k' -2- (V + v')

200
;low invoking equation ( C 2 ) and noting that the product of two f i n i t e poly-

non$als may be written as

where

j-0
J
e q u a t i o n ( C 4 ) becomes

Equation ( C 8 ) is a n e x p l i c i t a l g e b r a i c e q u i v a l e n t o f e q u a t i o n ( 6 . 1 9 ) f o r

a Morse o s c i l l a t o r , and t h e r e d u c e d i n t e g r a l t o b e s o l v e d is r e a d i l y a p p a r e n t .

Severalexactanalyticsolutionsofequation ( C 8 ) havebeenobtained i n the

p a s t ,b u to n l yf o rs p e c i f i cv a l u e so fn .F o re x a m p l e , Herman and S c h u l e r g 8

found a s o l u t i o n f o r n = 1 t h a t may b e w r i t t e n as

(1)
r w' - re
L 6w' " v ' v! ( v '
NavL - r v( k-) '(k' -v
v)T(k' - V'
v) - 1) v- r(k' (c9)

wherev' L v. Heaps andHerzberg"extendedthesolutionto n = 2 and

i n d i c a t e d a p r o c e d u r ef o ro b t a i n i n gs o l u t i o n sw i t hl a r g e rn . However, t h e

f o r m u l a t i o nf o r n = 2 is e x t e n s i v ea n dt h ei m p l i e df o r m u l a t i o nf o rl a r g e r

n a p p e a r si m p r a c t i c a lf o rt h er e q u i r e dc a l c u l a t i o no f numerousn terms.

G e n e r a l i z a t i o n of t h es o l u t i o n sf o ra r b i t r a r y n a l s oa p p e a r si m p r a c t i c a l .

Hence, f u r t h e r c o n s i d e r a t i o n s o f e x a c t a n a l y t i c s o l u t i o n s t o e q u a t t o n (C8)

were abandoned.The i t e r a t i v e numerical procedureofCashionloo was a l s o

r e j e c t e df o r similar r e a s o n s .I n s t e a d , w e s e e ka na p p r o x i m a t ea n a l y t i c

solutionbasedontheobservationthattheintegrand i n e q u a t i o n ( C 8 ) is a

201
 I

localized .function,
. , I . ,.confined;
to a.narrow, . .. :z of
range ,
... . .. .. X .is
when .
. , !. :.
..,.large,.
,
.,

Since the . .of

. X
yalue_; ,. is., dominated
. - . by . ,parameter k'
the , , . , and anharmonicify
. ;... ".:

is a second-order
, . . . . feature
. . . , o f all
, diatomic
.
..
. .
. ,.. k' , is always
molecules .. i .. .
large
., !.,
.
compared to unity. Hence an ,. . +.>>
approximation.based
- on
. . .
1. will
, .
be. : generally
I. .
applicable.

The generality of the approximation to be made is demonstrated in a

sense: by.writing,the
. . integral in equation (C8) in the generalized
. I. , , .. form:
..

where, U ( Z ) (c10).
is an arbitrary function. The integration,, of .equation

by parfs proceeds according

. . to . .

.. .

. I = u(z)uiz) /I -fm
0 0
dz
u(z) dz

where

and the integral in equation (C12) is indefinite. To evaluate equation (C12),

tb the series solution

repetitive integration by parts leads
. ..

which may be recognized as the asymptotic expansion for the incomplete

gamma function73:

202
Equation (C14) is an exact r e l a t i o n , b u t :it d o e s n o t ' s i m p l i f y t h e s o l u t i o n 'of

e q d t i o n (C11). e now s e e k an a p p r o x i m a t i o nt o
W u (z) t h a t is i n t e g r a b l e in
e q u a t i o n (C11). The n a t u r e of t h e . a p p r o x i & t i o n is ' i n d i c a t e d i n f i g u r e C. 1.
. .
Note"in f i g u r e C.l(a) t h a t t h e d e r i v a t i v .e . .
. . .

du(z) ~ e-zza
di

i8 v e r yl o c a l i z e df o rl a r g e a. It h a s maximum a t z - a and a h a l f - w i d t h
at a h a l f - h e i g h t o f Adz = m.Thus, t h er a n g e of t h e i n t e g r a n d i n

e q u a t i o n (C11) becomesnarrower as a i n c r e a s e s .N o t i n gt h e s ef e a t u r e s

o fd v ( z ) / d za n dt h ef a c tt h a t u(-) = 0 fromequation (C14), t h ef u n c t i o n

u(z)approaches a s t e pf u n c t i o n as s k e t c h e di nf i g u r eC . l ( b ) . Thus, w e can

approximate u(z) by i n t r o d u c i n gt h eH e a v i s i d e s t e p function:

t u

F i g u r e C.l.- P r o p e r t i e s of ' u (2) and its d e r i v a t i v e hu(z) /dz - a

z e
-2
.
203
and writing

where

u(0) = - r ( a
- + 1,O)
= -r(a + 1 )

f r o mt h ed e f i n i t i o no ft h e gamma function.73Hence, w e h a v e ,f o r a >> 1,

S u b s t i t u t i n ge q u a t i o n (C17) i n t o t h e e x p r e s s i o n f o r I ( a ) by equation ( C 1 1 )

a n di n v o k i n gt h es t e p - f u n c t i o np r o p e r t i e st h e nl e a d st o

Equation (C18) i s a g e n e r a l i z e da p p r o x i m a t es o l u t i o n of e q u a t i o n (C10)

f o ra r b i t r a r y ~ ( z )w i t ho n l yt h es t i p u l a t i o nt h a t a >> 1. It may b e

a p p l i e dt ot h es o l u t i o no fe q u a t i o n (C8) f o r X >> 1 w i t ht h er e s u l t :

From t h e d e f i n i t i o n o f X givenbyequation(C6), w e see t h a tt h er e q u i r e -

ment, X >> 1, i s m e t when

Since k' is always much l a r g e rt h a n 3 , t h ea c c u r a c yo fe q u a t i o n (C19) w i l l

depend p r i m a r i l yo nt h e sum v+v' and w i l l d e c r e a s e as t h e sum i n c r e a s e s .

Correspondingly,theaccuracyofequation (C19) i s nearlyindependentof n

204
s i n c e i t s d e r i v a t i o n was d o n e f o r a n a r b i t r a r y f u n c t i o n u ( z ) , i n t h i s case,

e q u a t e dt o[ 2 n ( k ' / z ) l n . Thus, w e c a nu s et h ee x a c ts o l u t i o nf o r n = 1

givenbyequation (C9) t o e v a l u a t e t h e a c c u r a c y o f e q u a t i o n ((219).

An i n s t r u c t i v e f i r s t s t e p i n a s s e s s i n g t h e a c c u r a c y o f e q u a t i o n (C19)

i s t o examine i t s v a r i a t i o n w i t h k ' . We do so most e a s i l y by c h o o s i n gt h e

s i m p l e s ta n dm o s tf r e q u e n t l ya p p l i e d case of v' = 1 and v = 0. The exact

s o l u t i o nf o r n = 1 is then

r:;) [exact] =
-vkl - 3 1
aL k' - 2

w h i l ee q u a t i o n (C19) g i v e s

r") [approximate] =
01 aL

The r e l a t i v e e r r o r i s simply

E r r o r = (k' - 2)Lnt: I -1
Sample e r r o r v a l u e s are t a b u l a t e d below f o r some diatomic molecules covering

a broadrangeof k'.

Species k' aLri:) [exact] Error

-0.1660 37.25 0.0144

co 161.22 -.0790 .00 32

N2 163.23 -.0785 .00 31
Br2
302.05 -.0576 .0017

Comparisons f o r H2 ( t h ew o r s t case) a t h i g h e r v and v' (smaller X) a r e

shown i n f i g u r e C.2. As t h e f i g u r e shows,equation (C19) i s a c c e p t a b l y

accurateforsingle-quantumtransitions ( i . e . ? v'-v = +1) i n H2 f o r a l l

205
 X
A
:C
T
, EQ.(C.9) EQ.
APPROXIMATE, (C.19)

.'

I I I I I
4 8 12 16 20
V

Figure c.2.- Radial integrals and their approximation for H,;

k' = 37.25, a L = 0.509.

initial eigenenergies a t l e a s t up t o h a l f t h e d i s s o c i a t i o n e n e r g y o f H,

implied by t h e Morse p o t e n t i a l . For o t h e rm o l e c u l e sw i t hl a r g e r k', a much

larger fraction of the total number of v i b r a t i o n a l s t a t e s w i l l b e t r e a t e d

a c c u r a t e l y by e q u a t i o n ((219).

The f. i. ,n. .a -l . consequencesofusingequation (C19) t o approximate r (n)

W'

are shown i n f i g u r e C . 3 where, again using H2 as the worst example, we

compare t h e r a d i a l matrix element (J:, computed usingequation(C19),with

Rw
numerically exact values obtained from a Gauss-Laguerre quadrature solutionlo l-lO3

ofequation(6.19).Thiscomparisonthenencompassesvaluesof r (n) for a

W'

widerangeofn. Recall t h a t small J v a l u e sc o r r e s p o n dt o small changes

i n a n g u l a r momentum s i n c e I R' -R I < J < R + R; w e showed i n c h a p t e r 6 thar:

small I R'-% I contribute most to the energy-transfer process. As f i g u r e C. 3

206
 20

IO

IO"

10-2

10-3
0 2 4 6 8 IO
J
Figure C.3.- Exact and approximate radial matrix elements He;
for
k' = 37.25, aL = 0.509.

illustrates, equation (C19) is exceptionally accurate for small J where .:

(J) is the largest and most effective. Furthermore, the accuracy is not
R*'
strongly degraded even for large v where r (n) is poorly approximated.
W'
Finally, in applying equation (C19) in a numerical calculation
with

large k' and increasing v+v',we find that the practical limit to its use

is not due to the error of the approximation but rather loss

to the
of

numerical precision. More specifically, when k' is large, as for CO or N p ,

the approximation is basically very accurate to v+v' < 150, thus including

single-quantum transitions from initial states to v = 75. However, the terms

in the summation of equation

(C19) alternate in sign
and the numerical range

207
 IIIIIIII Il 1 I 1 Il II I1

between the largest term and the final value sum

of can
the exceed the largest

number (with all digits significant) possible in most .computers (i.e., as

v+v' increases, we require decreasing differences between increasing numbers).

For example, using

a CDC-7600 computer with 28 digits in double precision,

meaningful values of r (n)

from equation (C19) for CO (k' = 161.22) were
V,v+l
obtained only up to v < 12 before all significant digits were lost. The

numerical quadrature solutions were developed to obtain matrix elements for

larger v. However, the orthogonality properties of r (n) are retained in

W'

the approximation and they may be used to at least monitor the numerical

precision when using equation (C19). To doso, one simply calculates

or the equivalent surviving terms,

v"v'
Dr(X+s+l) = O
S
s=o

concurrently with r(n) The precision with which equation (C22) is

W'
satisfied i s then a measure of the precision obtained with equation (C19).

208
 APPENDIX D

SPHERICAL MATRIX ELEMENT INTEGRAL

A general definition of the spherical matrix elements is given by

equation(6.15) as

where 6 is d e f i n e d by f i g u r e6 . 1a n d PJ i s a Legendresphericalpoly-

nomialoforder J. I ns e c t i o n 6.1.2.2,thesphericalharmonic wave func-

tions of a r i g i d r o t o r are t h e n i n t r o d u c e d a n d t h e matrix e l e m e n t s t a k e t h e

specific integral formgive by equation(6.21) as

whereangles 8 and $ are p o l a ra n g l e s( a l s od e f i n e di nf i g .6 . 1 ) . The

purposeofthisappendix is t o d e r i v e a n a n a l y t i c s o l u t i o n o f e q u a t i o n ( 6 . 2 1 )

using the properties of s p h e r i c a l h a r m o n i c f u n c t i o n s commonly a p p l i e d i n

a n g u l a r momentum t h e o r i e s . 04,

We b e g i n by n o t i n g t h a t e q u a t i o n ( 6 . 2 1 ) is s h i l a r t o t h e i n t e g r a l of

three spherical harmonics for which the solution i s known t o b e (Edmonds, l o 4

p. 63):

2a, + 1) (2R2 + 1) (2R,+ 1)

The bracketsymbols are Wigner 3-j symbols.Equation(6.21) may be made t o

c o r r e s p o n dt oe q u a t i o n ( D l ) by converting Yz,m, ( e , $ ) t o i t s complexconju-

gate using the spherical harmonic property (Rose, lo' p.241) :

2 09
and by e q u a t i n g Y
J, 0
(6,O) t o a new s p h e r i c a lh a r m o n i ci n terms of 8 and (p.
To accomplish the l a t t e r , w e recall t h e a d d i t i o n t h e o r e m ( R o s e , l o 5 p. 60) :

m
wheretheanglesinequation (D3) are r e l a t e d by

COS 6 = COS 8
1
cos 0
2
+ sin el s i n 8, - (p2)
(D4)

However,from f i g u r e6 . 1 , 6 is r e l a t e dt ot h ep o l a ra n g l e si ne q u a t i o n( 6 . 2 1 )

by

so t h a t , by a s s i g n i n g

el = n/2

e, = e

the addition theorem may b e w r i t t e n

El
With t h e a i d o f e q u a t i o n s (D2) and ( D 5 ) , t h e i n t e g r a l i n e q u a t i o n ( 6 . 2 1 ) may

now b e c o r r e l a t e d w i t h e q u a t i o n (Dl), givingthesolution, by i n s p e c t i o n , as

Equation (D7) is f u r t h e r s i m p l i f i e d by n o t i n g t h a t t h e 3-j symbol coupling

t h ep r o j e c t i o n states m' ,E and m i s nonzeroonly if

210
Hence t h e summation o v e rr e d u c e st o a s i n g l e term and t h en a t r i xe l e m e n t
. .

becomes

(D9)
Equation (D9) is t h e d e s i r e d a n a l y t i c m a t r i x e l e m e n t e x p r e s s i o n , b u t

it i s i n a s y m b o l i c n o t a t i o n t h a t r e q u i r e s f u r t h e r r e d u c t i o n t o o b t a i n a n

a l g e b r a i ce q u a t i o ns u i t a b l ef o rc a l c u l a t i o n . An a l g e b r a i c form w i l l a l s o

a l l o wt h ec l a s s i c a lt i m e - d e p e n d e n t terms introduced by E ( t )t ob ei s o l a t e d .

To achieve an algebraic formula, we f i r s t e v a l u a t e t h e f u n c t i o n

Y:$~/2,5). A comparisonoftheRodriguesformulaforanassociatedLegendre

polynomial, Py(x) , with the definition of YRm(a, B) , shows t h a t t h e two are

r e l a t e d by(Edmonds, l o 4 p. 24)

Thus, w e have

+ 1 ( J - iii)!
IT ( J + E)!
1 ' I 2 i€i
'J(O) e
-iiilE (t)
(D11)

r( J + i + l )
P
(: 0) = J;; cos[:(J - 2

Equation (D12) may b e r e d u c e d t o s i m p l e r a l g e b r a i c terms by n o t i n g t h a t

since J and IPI are i n t e g e r s ,t h ec o s i n e t e r m h a st h ep r o p e r t y :

211
 i14 [
J-iii
(-1)" for J. +ii even
c o s [;(J - = (Dl31
0 f o r J 5 odd

Hence,nonzero matrix elements are o b t a i n e d o n l y f o r v a l u e s o f J 5 even.

With t h a t s t i p u l a t i o n , t h e gamma f u n c t i o n s i n e q u a t i o n (D12) are a l s o

r e d u c i b l e as follows:Define a parameter z so t h a t

Then z = (J + m)/2 i s alwaysanintegerbecause J + iii i s a ne v e ni n t e g e r .

With i n t e g e r z , t h ed u p l i c a t i o nf o r m u l af o r gamma f u n c t i o n sg i v e s 7 3

or

so that

r (J + ii + 1)

Hence,nonzerovaluesofY:E(~/2,5) a r e g i v e nf o r J f m evenby

With equation(D16),thetime-dependent terms are e a s i l y i s o l a t e d i n t h e m a t r i x

elementformula by d e f i n i n g a new matrix with constant elements given by

212
Again, t h e s t i p u l a t i o n s o n da
(J)
ml I are t h a t J kii i s evenand iii = m' - m.

Equation (D9) may t h e n b e w r i t t e n

thusobtainingtheresultsgiven by equations(6.22)and(6.23).

Equation (D17) hasbeenmaintained i n terms of t h e s y m b o l i c 3-j

coefficients to simplify the notation, but they may b e e v a l u a t e d by t h e well-

known f o r m u l a s t o f o l l 0 w ~ l~o~59:

The c o e f f i c i e n t (T :) is nonzeroonlyfor L E E' +J + R even. With

that stipulation,

= (-l)L/2[(L - 2E') ! (L - 25) ! (L -

(L + 1)!

(L/2) !
(L/2 - E')! (L/2 - J)! (L/2 - E)!

Forevenvaluesof R' +J+ R, w e c a n a l s o e q u a t e

where C(RJR':m ii m') i s a Clebsch-Gordan c o e f f i c i e n td e f i n e db yR o s e , l o 5

(p. 39), w i t h a c o n v e n i e n ta l g e b r a i ce x p r e s s i o n . The r e s u l t t h e n l e a d s t o

213
 . .

where v rangesover a l l integervaluesgivingnonnegativefactorial.az-gu-

ments. S i n c e t h e indice constraints giving nonzero values of the vector-

. .

c o u p l i n gc o e f f i c i e n t s (3-j symbols) are

G=m'- m

t h e sunnuation limits i n e q u a t i o n (D20) are t h o s e t h a t d e f i n e t h e n a r r o w e s t

range
of u within

Mini,mum I, 2 0 ,J - R + m'
Maximum u 5 J + R' + R , 11' + m'
Equations (D17) t o (D20) are s u f f i c i e n t t o c a l c u l a t e TR,m,am
(J) for a l l

J, a ' ,m' R ,m combination6 satisfying equation (D21) and

R' +J + R even

J Hi even

A l l other matrix elements are zero.

214
 APPENDIX E
.. . . - .
. . ... . '. , .. . .
.
I . .
.
ANALYTIC TRAJECTORY EQUATIONS FOR NONZERO IMPACT PARAMETER
!,. :. . . . . .
. I

6 by equation ( 6 . 3 3 ) as
We have defined a trajectory function in chapter
.. .-I
. . . . , L , " . . , . .I
. ... , . .t . . , .

IC. '3),: .

- L ' ' r ' . < . ,

where the constants,. are specified by the 'sphericdiiy averaged interaction'
*

potential
I
I

Then, to solve the:set of coupled dynamical equations describing the collision,

U(b,t) must be determined explicitly in terms of timet. One approach would

be to numerically integrate the classical ..

. .equation
trajectory given in appen-
dix B as

6 , there are considerable advantages provided

but, aswe point out in chapter

by an approximate analytic description of U(b,t) that benefit both the

remaining numerical analysis and future analytic descripclons of the,collision

dynamics. In this appendix, we therefore develop an analytic form

of U(b,t)

by following the of Hansen

work and Pearson.
lo6

An indication of the functional

. I . .
form
,
of U(b,t) is obtained by noting that
1.

equation (E2), with the potential given by equation (El), may be solved
.' * , .'
exactly for b = 0. The result is

2 fit
= sech (E)
b= 0

where Zo denotes the distance of closest approach. Furthermore, at closest

approach for b = 0, all the initial kinetic energy is converted to potential

energy so that
-V = E, leading to
215 !
 II I I I 11111 I1

(E2)
In view of equation (E3), the primary nature of solutions to equation

for nonzero impact parameters should be represented by

- [I(b,t) - Io(b) ]/L) = sech2[ab(b,t) E]

where ab(b,t) is a slowly varying function of both b and t that can be

approximated by a low-order expansion.

By solving equation (E2) numerically, we can obtain the exact values of

ab(b, t) required to satisfy equation (E5). Some sample results are tabulated

below for a representative collision energy and for small- and large-impac

parameters.

TABLE E1.- EXACT VALUESOF ab (b,

t) FOR E/Vii =

b/L iit/L V/E ab(b,t)

1.2 0 0.994 0.99

6 .01 .995

8 0 .38 .70
6 .015 .74

16 0 ,0010 .35
6 .0004 .38

Note that when the change in ab(b,t) with t becomes noticeable, the inter-

action potential is extremely small. We can therefore approximate ab(b,t)

without introducing significant error in the collision dynamics by assuming

ab (b,
t) .
ab (b,O) Then, expanding both sides
of equation (E5) about t = 0,

we obtain, to first order,

1 - [Z(b, t) - -x0(b) ] /L = 1 - (ab6t/2Ll2 (E61

216
Similarly,

Z(b,t) = Zo(b) + t(g) t=O

+ -$(?3)
at2 tro

From equation(E2),

= O
=O

and

Since (aT/at)t=o = -v/L from equation (El), equation (Ed) finally leads to

Note that Z0(b) must still be computed by iteratively solving equation

(E2)

for t = 0. However, as we show in figure6 . 6 , Zo(b) is closely approximated

by equation (E4) when the impact parameter

is small. Similarly, when the

impact parameter is large, the trajectory is nearly a straight line and

path
-xo(b) * b. In that case, equation (E8) becomes

a p , O ) = J2L/b (E91

All three cases are compared in figure E.l, where we see

a completely
that

0 4 8 12 16 20
b/L

Figure E . 1 . - Trajectory coefficients for E/AVii

=

217
 -
xo(b = 0) from equation (E4) for
analytical approach would be to compute

increasing b until it gave values of ab equal to those from equation (E9).

-
Beyond that point, a better approximationis to assume x. a b. In that case,

U(b,t) 0 according to equation (6.33) and the interaction may be considered

negligibly small.

218
 APPENDIX F

SYMMETRIES OF VIBRATION-ROTATION MATRIX ELEMENTS

AND THEIR COMPACT COMPUTER STORAGE

Experience with the collinear collision model made clear the facts that:

the basis set required afor

three-dimensional vibration-rotation model would

be large, it would vary in size with the initial conditions, and it should

minimized for computing economy.A basic criterion of the computational

. .

scheme was therefore

to permit an arbitrary basis set of vibrational and rota-

tional eigenstates to be specified as part of the input information. Conse-

quently, the calculation requires of time-

a large and variable number

independent matrix elements,VV,R,m,vRm. Since the matrix elements are con-

compute them in advance

stant in time, the obvious procedure towas of the

dynamical solution and store them in the computer memory.

When specifying the basis set in problems of this nature, the available

size of accessible memory can be as severe

a limitation as the computing time

required. In large time-sharing systems, the operating cost

is affected by

often not
both factors, while, in smaller systems, adequate memoryis volume

available. Hence the programmer's task becomes one

of minimizing the memory

of the largest
volume that must be allocated to accommodate matrix elements

basis setof interest. Since the allocation must usually be done in advance

of any input information, the storage scheme must also be optimized in advanc

Each matrix element is identified by six quantum numbers for which the

simplest storage scheme would a

besix-dimensional array. However, advance

memory allocation for such an array would be extremely wasteful because each

219
dimension would have to value of interest. For example,
be set to the largest

suppose we choose the random basis set:

. .

i v
- -
i -Ri
1 4 3

2 4 1

3 4 0

4 5 2

where i is an index identifying the state, and vi and Ri are the vibra-

tional and angular momentum quantum numbers specifying the state. .If vm,Rm

are vm
represents the largest values to be considered, then there + 1, 1, +1
possible values of v, 11 and 23, +1 values of m. To accommodate the

example, let vm,Rm = 5,3. Then the array wouldbe dimensioned

V(v'R'm'vRm) = V(6,4,7,6,4,7), thus allocating 28,224 memory elements, while

by the sample basis

only 256 are filled set above.

On second thought, a more efficient storage scheme i

is based on the index

identifying each state and %, the projection quantum number. Two small 1-D

(one-dimensional) arrays, vi(i) and Ri(i), may be established to give the

v,R quantum numberswhen needed and the matrix elements are stored in a square

2-D array,
R 'm' vtm
= V( j ' ,j) , where j is computed from

i
j = (2gk + 1) - R
i
+ mi (F2)
k= 1
is illustrated
Such a matrix element array for the example basis set schemati-

cally in figureF.l. The array dimensions, allocated in advance, are

now

required to be only as largeas the total numberof differential equations

that can be solved in a reasonable computing time. Thus, the storage alloca-

tion and the computing time limits are kept compatible. As.,an example, suppose

220
 11

Figure F.1.- A representation of the matrix elementsV v ~ ~ ~ m * vcorrespond-

em
ing to the sample basis set, equation(Fl). Each group, i or j, repre-
sents a pair of quantum numbers, vi and Ri. The matrix element is then
identified by relating V V ~ ~ ~ mto~the
v ~array
m V(i,mi,j,mj). The
shaded squares are locations containing zeros. The filled circles
denote primary elements, unrelated by symmetry. The open squares and
'open circles 0 are elements relatedto the primary elements by the
symmetry equations (F9) and F11). The open circles are additional ele-
ments included in the index equation, equation (F17), and stored with the
primary elements in memory.

to 16.
that the maximum computing time limits the total number of states That

limit would then encompass the example basis set and require a matrix element

array with 256 elements.

i While the preceding storage scheme

is a notable improvement, it is still

extremely wasteful. Closer examination of the sample matrix element array in

figure F:l reveals that, as a result of the constraints on rotational state

coupling given by equations (6.24) and (6.251, almost half of the elements are

zeros. In addition, -approximately three quarters of the nonzero values are

221
 numbers with opposing but duplicate magnitudes, as
signs a consequence of the

. symmetries of Hence, there is an obvious opportunity to further

: - reduce the storage requirements by storing only the elements of unique a

, nonzero magnitude. Such a scheme requires additional computing of indices to

. -relate an arbitrary set of quantum numbers, v'R'm'vRm, to the storage indice

containing the appropriate matrix element. But, for large basis sets, that

is offset bya reduction

additional small effort in the number
of elements

that must be computed and by the savings in storage. We may use, as an

" "illustrative example, the largest basis set represented in this It

study.
was

for a heteronuclear molecule (CO) containing two vibrational manifolds with

rotational states from R = 0 to 10 in each one. Thus,242 states were

. included and a V(j',j) array of 58,564 elements would have been required.

However, by storing only the unique and nonzero matrix elements, the storage

I requirement was reduced to14,883 elements. While the storage requirement was

still large, the difference decided between possible and impossible storage

allocation. The remaining paragraphsof this appendix are therefore devoted

"

to a study of the symmetry properties

of VVIR,m,vRm needed to select the
0 -

unique elements anda derivation of the index equations for locating the

matrix elements in
a reduced storage scheme.

F. 1 SymmetriesofVv, vRm

The symmetry properties ofVv,R,m,vRm are revealed by the terms defin-

ing it. According to equation

R'+R
-
$1 m' vRm
c

222
 where

and f(r,J) is an algebraic function of r and J given in equation (6.16). 4

We first note that the vibrational states are freely interchangeable

because the vibrational wave functions are purely real and not operated upon ,

by the algebraic function f(r,J). Thus, equation (F6) may be rewritten to

give

(F7) . -
for all J.

Next, the summation limits in equation (F3) areto seen

be unaffected by

an interchange of R and 2 ' . Hence, all the remaining symmetry properties of

are determined entirely by the rotational coupling Aterm,
(3)
m' '
v R 'm' vRm
Furthermore, having generalized the vibrational symmetry, only three possible
"
elementary symmetry operations remain:(1) an exchange symmetry between rota-
I)

tional states to relate(J)

JQtmlem and A R(m
J)R l m t ,
(2) a sign reversalof m only,

and (3) simultaneous sign reversals of m and

m'. All other operations would

correspond to combined applications of the above. In the following, we deal .:

with exchange and sign-reversal symmetries separately.

223
yExchange F.l.l .. . I .,
The relation dk,m,
of (J) Rm and - k k(,J
Q), m , is easily shown in a :'
general

6,
fashion by starting with its definition in symbolic notation. From chapter

kJ) is
equivalent
to
k'm' Rm

6 and
where the combination of terms containing the time-dependent variables,
-Q, render the result constant in time. (Note that the bracket notation in

eq. (F8) implies the integration over all configuration space.) Again,

the operator PJ(cos 6) is algebraic and hence not operable on the wave func-

tions. Thus, equation (F8) is unchanged when rewritten as

But equation (F4) shows that the rotational coupling terms are alwaysso real
that *1,kJ[ (J) = (J) leading to A (J)
dQmQ'm' m m, . Correspondingly,
R r m -rdQmQ
R(J>

F. 1.2 Projection-State Sign-Reversal Symmetry

As indicated previously, sign reversal may be implemented in two ways.

The first, a sign reversal of

m alone may be immediately dismissed as an

unsymmetric operation by noting that it would induce a change in the magn

of 'm via equation (F5) and thereby leadto different magnitudes for
(J)
Jk'm'Rm
(J)
and JE'm'e,-m
. The second case is a simultaneous sign reversal of

224
 -

I -

both m and m'. Only the sign of E is then reversed and equation (F4)
. .
leads to

The corresponding 3-j symbol symmetry is given by O4 (p. 47) as

Edmondsl

but t' + J + !t (i.e., R1 + R2 + R 3 in the above equation) must be even to

obtain nonzero values of (x t ) in equation (F4). Thus, the ratio of

3-j symbols in equation(F10) is always unityand we are led to the final

result :

With the symmetries given by equations

(F9) and (Fll), one choice of pri-

mary matrix elements is illustrated in figure

F.l by the filled circles. In

the notation of figureF.l, V(i,mi:j,+m ) are included for each i and all
j
from -Ei to zero. All j and +m are included that fall to the right
"i j
of the diagonal,with the exception of those related to preceding in the
"j
same row by synmetry. All other matrix elements (indicated by open spaces and

open circles in fig. F.l) are then obtained by the symmetry relations,

equations (F9) and (F11) .

F.2 Primary Matrix Element Storage

The remaining task is

now to devise a scheme of indexing the primary

matrix elements so that they may be stored and retrieved using the identifier

mi, j , mj).
set (I, The method chosen hereis to index them sequentially from

1eft.to.right in figureF.l, starting with the top row and continuing, row by

225
row, toward the bottom. The primary elements may then be stored
a minimum
in

memory volume by computing the indexP ( i , m and locating them ina'l-D

j,m
j 2,
array, ~(p). Similarly, the matrix elements are retrieved during the dynami-

,j ,m ) and
cal solution by again computing P(i,m applying the symmetry equa-
j j

explicitly in terms of the identifiers to complete the storage scheme.

Before developing the index equation, we first note that the formulation

will be somewhat simplified weifslightly relax the requirement aZZ

that

matrix elements related by.symmetry be excluded

from.theprimary set. Very

little redundancy is introduced by reinstating the few excluded matrix ele-

ments to the right of the diagonal in figure F.l in rows mi -

-ti I where
< 0.

Such elements are indicated in figure F.l by open circles. With those ele-

ments included, we compute P(i,mi,j,m.) by first defining the following

J
component terms:

An operator is required to be identified with eachrow

(i,mi)
and with

the properties

Then the total number of primary and symmetric nonzero elements in row (i,m

is

where I is the total numberof (vi,a.)

1
states in the basis set. Similarly,

the numberof nonzero symmetric elements

to the leftof the diagonal in row

226
 i-1

so that the total number p of

r i m a r y elements in row (i,mi) is
I

The numberof rows preceding row (i,mi) is

so that the total number

of primary elements in rows preceding row )(i,m
i is
then

Now choosinga specific element in row (i,mi), the number of nonzero primary

and symmetric elements preceding V(i,mi,j,m.) is

3

while those symmetric elements to the left of the diagonal are again given

equation (F12) but rewritten as

i- 1

The difference in the two terms above is then the

of primary
number elements

preceding V(i,m ,j,m ) in row (i,m ), given by

i j i
i- 1

227
The index of V(i,mi,j,m ) is nowa combination of terms (F15) and (F16) with
J
the result

P(i,mi,j ,mj) = 1 + (R
j
- Ri + mj -
r=
mi)/2 + 5
k-i
(Ek + 6i,m) + n(y)
1
N(ry4)

(F17)
Equation (F17) requires that j 2 i. The identifiers may be exchanged to read

P(j ,mj,iYmi) if i 1 j . Note that the summations in equation (F17)

may also
be reduced to more efficient forms for computer calculation.

228
, .

REFERENCES

1. H. Kallmannand F. London, Zeit. Physik. Chem. B2, 207(1929).

2. 0. K. Rice, Phys. Rev. 38, 1943 (1931).

I

3. C. Zener, Phys. -
Rev. 38, 277 (1931); Proc. Cambridge Phil. SOC. 29,
136(1933).

4. L. Landauand E. Teller, Physik. Z. Sowjetunion 10, 34 (1936).

5. K. F. Herzfeldand F. 0. Rice, Phys. Rev. 3 l , 691(1928).

6. K. F. Herzfeld and T. A. L i t o v i t z , Absorption and Dispersion of Ultra-

sonic Waves, Academic Press(1959).
7. H. A. Betheand E. Teller, "Deviationsfrom Thermal E q u i l i b r i u m i n Shock

Waves," AberdeenProvingGround, B a l l i s t i c R e s . Lab. Rept. X-117

(1945).

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