Phys4011 W13 PDF

PHYS 4011, 5050:
Atomic and Molecular Physics
Lecture Notes
Tom Kirchner1
Department of Physics and Astronomy

York University
April 7, 2013
1 [email protected]
Contents
1 Introduction: the field-free Schrödinger hydrogen atom 2

1.1 Reduction to an effective one-body problem . . . . . . . . . . 2
1.2 The central-field problem for the relative motion . . . . . . . 4
1.3 Solution of the Coulomb problem . . . . . . . . . . . . . . . . 5
1.4 Assorted remarks . . . . . . . . . . . . . . . . . . . . . . . . . 13
2 Atoms in electric fields: the Stark effect 16

2.1 Stationary perturbation theory for nondegenerate systems . . 17
2.2 Degenerate perturbation theory . . . . . . . . . . . . . . . . . 22
2.3 Electric field effects on excited states: the linear Stark effect . 24
3 Interaction of atoms with radiation 29

3.1 The semiclassical Hamiltonian . . . . . . . . . . . . . . . . . . 29
3.2 Time-dependent perturbation theory . . . . . . . . . . . . . . 32
3.3 Photoionization . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.4 Outlook on field quantization . . . . . . . . . . . . . . . . . . 44
4 Brief introduction to relativistic QM 58

4.1 Klein-Gordon equation . . . . . . . . . . . . . . . . . . . . . . 58
4.2 Dirac equation . . . . . . . . . . . . . . . . . . . . . . . . . . 60
5 Molecules 70
5.1 The adiabatic (Born-Oppenheimer) approximation . . . . . . . 71
5.2 Nuclear wave equation: rotations and vibrations . . . . . . . . 74
5.3 The hydrogen molecular ion H+ 2 . . . . . . . . . . . . . . . . . 77
1
Chapter 1
Introduction: the field-free

Schrödinger hydrogen atom
The starting point of the discussion is the stationary Schrödinger equation
ĤΨ = EΨ (1.1)
for the two-body problem consisting of a nucleus (n) and an electron (e).
The Hamiltonian reads
p̂2n p̂2e Ze2
Ĥ = + − (1.2)
2mn 2me 4πǫ0 |re − rn |
with
mn = N 1836me ; me ≈ 9.1 × 10−31 kg
and N being the number of nucleons (N = 1 for the hydrogen atom itself,
where the nucleus is a single proton).
The first step is to separate this two-body problem into two effective
one-body problems.
1.1 Reduction to an effective one-body prob-

lem
• Consider the (classical) coordinate transformation
(re , pe , rn , pn ) −→ (R, P, r, p)
2
3
definitions : M = me + mn ≈ mn
me mn
µ = ≈ me
me + mn

R = mn rnM+me re ≈ rn 
center − of − mass
 motion
P = pe + pn = M Ṙ ≈ pn

r = re − rn 
relative
motion
p = µṙ = mn peM
−me pn 
≈ pe
• QM transformation analogously
(r̂e , p̂e , r̂n , p̂n ) −→ (R̂, P̂, r̂, p̂) (1.3)
insertion into Eq. (1.2) yields
P̂2 p̂2 −Ze2

Ĥ = + + V (r) , V (r) = (1.4)
2M 2µ 4πǫ0 r
= ĤCM + Ĥrel
Eq. (1.4) is the Hamiltonian of a non-interacting two-(quasi-)particle
system ֒→ can be separated into two one-particle problems:
ansatz : Ψ(r, R) = ΦCM (R)ϕrel(r) (1.5)
֒→ Schrödinger equations (SEs)

~2 2
ĤCM ΦCM (R) = − ∇R ΦCM (R) = ECM ΦCM (R) (1.6)
2M2
~ 2 Ze2
Ĥrel ϕrel (r) = − ∇r − φrel (r) = Erel ϕrel (r) (1.7)
2µ 4πǫ0 r
with E = ECM + Erel (1.8)
Equation (1.6) can be solved without difficulty:

֒→ ΦCM (R) = AeiKR  



1 free − particle
K = ~P

 motion


2 K2 
ECM = ~2M
4
Equation (1.7) can be solved analytically, but before we sketch the

solution we consider some general properties/features of the quantum
central-field (V (r) = V (r)) problem.
1.2 The central-field problem for the relative

motion
p̂2
Consider Ĥrel = + V (r) .
2µ
(1.9)
One can show that Ĥrel is invariant with respect to rotations, and therefore
commutes with the angular momentum operator
l̂ = r̂ × p̂. (1.10)
This is a manifestation of angular momentum conservation. In particular,

the operators Ĥrel , l̂2 , ˆlz form a complete set of compatible operators, i.e.,
[Ĥrel , l̂2 ] = [Ĥrel , ˆlz ] = [l̂2 , ˆlz ] = 0 (1.11)
֒→ they have a common set of eigenstates. The eigenstates of l̂2 , ˆlz are the
spherical harmonics Ylm .
֒→ ansatz ϕrel (r) = Rl (r)Ylm (θ, ϕ) . (1.12)
insertion into Eq. (1.7) for Hamiltonian (1.9) yields the radial SE
( )
p̂2r ~2 l(l + 1)
+ + V (r) − Erel Rl (r) = 0 (1.13)
2µ 2µr 2
~2
with p̂2r = − ∂r (r 2 ∂r )
r2
l̂2
and operator identity p̂2 = p̂2r + 2
r
(can be proven in spherical coordinates in coordinate space).
Useful definition : yl (r) = rRl (r) (1.14)

5
(1.13)
h l(l + 1) i
֒→ yl′′(r) + ǫ − U(r) − yl (r) = 0 (1.15)
r2
~2 ~2
Erel = ǫ, V (r) = U(r)
2µ 2µ
1.3 Solution of the Coulomb problem
The radial Eq. (1.15) is very similar to the one-dimensional SE. There are,
however, two important differences. First, the total (effective) potential con-
sists of two parts
l(l + 1) r→∞
Ulef f (r) = U(r) + −→ 0
r2
տ ′′ angular momentum barrier′′
(cf. classical central-field problem) Second, the boundary conditions are dif-
ferent.
a) Boundary conditions
• r −→ 0
|ϕrel (r)|2 = |Rl (r)|2|Ylm (θ, ϕ)|2 < ∞
in particular for r = 0
֒→ ’regularity condition’
yl (0) = 0 (1.16)
• r −→ ∞
1. Erel < 0 (bound spectrum)
Z Z ∞ Z
2 3
|ϕrel (r)| d r = 2 2
r Rl (r) dr |Ylm (θ, ϕ)|2 dΩ
Z0 ∞
= yl2 (r) dr < ∞
0
(square integrable solutions required)

r→∞
֒→ yl (r) −→ 0 (′ strong′ boundary condition)
6
2. Erel > 0 (continuous spectrum)

֒→ oscillatory solutions yl (r) for r −→ ∞

note: for Erel > 0 the solution leads to Rutherford’s scattering formula
(which is identical in classical mechanics and QM)
b) Bound-state solutions
definition : κ2 = −ǫ > 0
4πǫ0 ~2
a = ≈ 0.53 · 10−10 m
µe2
for µ ≡ me , a ≡ a0 is the ′ Bohr radius′
֒→ radial Eq. (1.15):

!
d2 l(l + 1) 2Z
− + − κ2 yl (r) = 0 (1.17)
dr 2 r2 ar
transformation: x = 2κr
d2 1 d2
֒→ =
dx2 4κ2 dr 2
!
d2 l(l + 1) λ 1
֒→ − + − yl (x) = 0 (1.18)
dx2 x2 x 4
asymptotic solutions:
1. x −→ ∞ !
d2 1
֒→ − yl (x) = 0
dx2 4
x x
֒→ yl (x) = Ae− 2 + Be 2
because of yl (x → ∞) = 0 ֒→ B = 0
7
2. x −→ 0 !
d2 l(l + 1)
֒→ − yl (x) = 0
dx2 x2
A
֒→ yl (x) = + Bxl+1
xl
because of yl (0) = 0 ֒→ A = 0 .
This consideration motivates the following ansatz

x
yl (x) = xl+1 e− 2 vl (x). (1.19)
Insertion into Eq. (1.18) yields a new differential equation for vl (x):
( )
d2 d
֒→ x 2 + (2l + 2 − x) − (l + 1 − λ) vl (x) = 0. (1.20)
dx dx
The square integrable solution of (1.20) (’Kummer’s’ or ’Laplace’s’ differen-

tial eq.) are known; they are the associated Laguerre polynomials:
p 2
X (p + k)!
Lkp (x) = (−) j
xj .
j=0
(p − j)!(k + j)!j!
More specifically:

nr = n − l − 1 ≥ 0
vl (x) = L2l+1
n−l−1 (x) ,
⇐⇒ n − 1 ≥ l
Z
with n ≡ λn = , n = 1, 2, ... (1.21)
κn a
The detailed treatment shows that the integrability of the solutions requires
Z
λ = κa to be positive, integer numbers −→ quantization of κ (i.e. quantiza-
tion of the energy)1
֒→ ynl (r) = Anl r l+1e−κn r Ln−l−1

2l+1
(2κn r)
1
P One
l i
finds the square integrable solutions of (1.20) explicitly by using the ansatz vl (x) =
i bi x and by taking the boundary (and regularity) conditions into account.
8
and properly normalized wave functions take the form
(n − l − 1)! l+ 1 l+2 √
ϕrel (r) ≡ ϕnlm (r) = 3 2 2 κn a
(n + l)!
× r l e−κn r L2l+1
n−l−1 (2κn r)Ylm (θ, ϕ) (1.22)
n≥0
≡ Rnl (r)Ylm (θ, ϕ) l ≤n−1
−l ≤ m ≤ l
The quantization condition (1.21) yields
~2 Z 2
Erel ≡ En = − n = 1, 2, ... (1.23)
2µa2 n2
Z2
≈ −13.6 eV 2 . (1.24)
n
The lowest-lying hydrogen eigenfunctions (’orbitals’):
n l m nr = n − l − 1 ϕnlm (r) −En

23 Zr
1 0 0 0 1s √1 Z
e− a RZ 2
π a
32 Zr
√1 Z Zr RZ 2
2 0 0 1 2s 4 2π a
2 − a
e− 2a 4
32 Zr
√1 Z Zr RZ 2
2 1 0 0 2p0 4 2π a a
e− 2a cos θ 4
23 Zr
RZ 2
2 1 ±1 0 2p±1 ∓ 8√1 π Za Zr
a
e− 2a sin θe±iϕ 4
with R = 13.6 eV
9
E s p d
0
n = 3
3 s 3 p -1 3 p 0 3 p 1 3 d -2 3 d -1 3 d 0 3 d 1 3 d 2
n = 2
2 s 2 p -1 2 p 0 2 p 1
n = 1
1 s
Figure 1.1: Energy spectrum of the Schrödinger-Coulomb problem. Note that

n→∞
the Coulomb potential supports infinitely many bound states (En −→ 0).
Degeneracy of energies (which depend only on n)
given n l = 0, 1, ..., n − 1
given l m = −l, ..., l
n−1
X
֒→ (2l + 1) = n2
l=0
−→ each energy level En is n2 -fold degenerate. Note that all central-field

problems share the (2l + 1)-fold degeneracy which originates from rotational
invariance. The fact that the energies do not depend on nr , l separately, but
only on n = nr + l + 1 is specific to the Coulomb problem (one names n
the principal quantum number and nr the radial quantum number, which
determines the number of nodes in the radial wave functions).
10
In QM, the wave functions themselves are (usually) not observable, but
their absolute squares are
ρnlm (r) = |ϕnlm(r)|2 = Rnl

2
|Ylm (θ, ϕ)|2
y 2 (r)
= nl 2 |Ylm (θ, ϕ)|2 . (1.25)
r
R
If ρnlm (r)d3 r = 1 one interpretes ρnlm (r)d3 r as the probability to find the
electron in the volume [r, r + dr]. For spherically symmetric potentials it is
useful to also define a radial probability density by
Z
ρnl (r) = r Rnl (r) |Ylm (θ, ϕ)|2 dΩ
2 2
2
= ynl (r) (1.26)
ρnl (r)dr is the probability to find the electron in the interval [r, r + dr]
Momentum space representation
So far we have worked in coordinate space, in which states are wave func-
tions ϕ(r). It is also possible — and insightful — to look at the problem
in another, e.g., the momentum space representation, which is connected to
the coordinate space representation by a (three-dimensional) Fourier trans-
formation. Using the Dirac notation one can obtain momentum space wave
functions by considering
Z
ϕnlm (p) = hp|ϕnlmi = hp|rihr|ϕnlmid3r
Z
1 i
= 3 e− ~ p·r ϕnlm (r)d3 r. (1.27)
[2π~] 2
To work out the three-dimensional Fourier transform one uses the expan-
sion of a plane wave in spherical coordinates
L
∞ X
X
e−ik·r
= 4π (−i)L jL (kr)YLM (Ωk )YLM
∗
(Ωr ) (1.28)
L=0 M =−L
11
with p = ~k and the spherical Bessel functions jL .

L
∞ X Z ∞
1 X
L
֒→ ϕnlm (p) = 4π 3 (−i) r 2 jL (kr)Rnl (r)dr
[2π~] L=0 M =−L
2 0
Z
∗ ∗
× YLM (Ωr )Ylm (Ωr )dΩr YLM (Ωk )
Z ∞
1 l
= 4π 3 (−i) r 2 jl (kr)Rnl (r)dr Ylm (Ωk )
[2π~] 2 0
=: Pnl (p)Ylm (Ωk ). (1.29)
Probability densities can be defined in the same way as in coordinate space
ρnlm (p) = |ϕnlm (p)|2

ρnl (p) = p2 Pnl
2
(p). (1.30)
Figure 1.2: Radial hydrogen 1s, 2s, 2p wave functions (blue) and probability
densities (red) in coordinate space.
The maximum of the 2p probability density is shifted to smaller r com-

pared to the 2s state. We can understand this qualitatively in the following
way. Both states 2s,2p correspond to the same eigenenergy. The 2s state has
a contribution at small r (the first lobe), for which the potential energy is
rather large as the nucleus is close. By contrast, the 2p state approaches 0
for small distances (remember the angular momentum barrier: only s states
12
do not approach zero for r → 0). To compensate for the stronger binding
energy of the 2s state at small r the 2p state has to have its only maximum
at smaller r compared to the second maximum of the 2s state.
Figure 1.3: Radial hydrogen 3s, 3p, 3d wave functions (blue) and probability
densities (red) in coordinate space.
Figure 1.4: Radial hydrogen 1s, 2s, 2p wave functions (blue) and probability
densities (red) in momentum space.
The number of nodes in momentum space and coordinate space is the

same. Note that the momentum profile of 2s is restricted to rather small
momenta. Loosely speaking, the inner lobe of the momentum distribution
corresponds to the outer lobe of the distribution in coordinate space: When
the electron is far away from the nucleus the momentum is relatively small
13
(and vice versa). This phenomenon is related to the uncertainty principle.

The inner lobe in coordinate space is rather sharp, whereas the outer lobe in
momentum space extends over a relatively wide range of momenta (and v.v.).
But note that this is not a rigorous argument, because the radial momentum
is NOT the canonical momentum of the radial coordinate, i.e., they do not
fulfill standard commutation and uncertainty relations.
Figure 1.5: Radial hydrogen 3s, 3p, 3d wave functions (blue) and probability
densities (red) in momentum space.
Check the Maple file hydrogen.mw for more details!
1.4 Assorted remarks

a) More (mathematical) details about the Coulomb problem can be found
in any QM textbook, in particular in [Gri], Chap. 4.1–4.3.
b) Hydrogen-like ions
We have solved not only the (Schrödinger) hydrogen problem (Z = 1),
but also the bound-state problems of all one-electron atomic ions (e.g.
He+ , Li2+ ,...) for Z = 2, 3, ... Note that En ∝ Z 2 .
c) Exotic systems
... are also solved
(a) positronium (e+ e− )

(b) muonium (µ+ e− )
(c) muonic atom (pµ− )
14
In these cases one has to take care of the different masses compared to
the hydrogen problem. Note that En ∝ µ = mm11+m m2
2
.
d) Corrections
The spectrum determined by Eq. (1.23) is the exact solution of the
Schrödinger-Coulomb problem, but not exactly what one sees experi-
mentally. The reason is that the Schrödinger equation is not the ulti-
mate answer, e.g., it has to be modified to meet the requirements of
the theory of special relativity. Therefore, corrections show up, which
lead to a (partial) lifting of the degeneracy. This will be discussed later
on.
e) Atomic units
So far, we have used SI units (as we are supposed to). In atomic and
molecular physics another set of units is more convenient and widely
used: atomic units. The starting point for their definition is the Hamil-
tonian
~2 2 e2
ĤSI = − ∇ − (1.31)
2me r 4πǫ0 r
(i.e., the one of Eq. (1.7) for Z = 1 and µ → me ). Four constants show
up in this Hamiltonian — way too many — and so they are all made
to disappear!
Recipe
• measure mass in units of me

• measure charge in units of e
• measure angular momentum in units of ~
• measure permittivity of the vacuum in units of 4πǫ0
In other words, atomic units (a.u.) are defined by setting me = e =

~ = 4πǫ0 = 1.
Consequences
• Ĥa.u. = − 12 ∇2r − 1
r
15
• length: let’s look at Bohr’s radius
4πǫ0 ~2
a0 = = 0.53 · 10−10 m = 1a.u.
me e2
• energy: let’s look at the hydrogen ground state H(1s)
~2
E1s = − = −13.6 eV = −0.5 a.u. = −0.5 hartree = −1 Rydberg
2me a20
• time: let’s do a dimensional analysis
distance distance × mass distance2 × mass

time = = =
speed momentum angular momentum
a20 me
֒→ t0 := ~
= 2.4 · 10−17 s = 1 a.u.
• fine structure constant (dimensionless)
e2 1
α= ≈ .
4πǫ0 ~c 137
In atomic units we have α = 1/c, i.e. c ≈ 137 a.u. Thus, one
atomic unit of velocity corresponds to 2.2 · 106 m/s. This is also
obtained by using v0 = a0 /t0 .
Chapter 2
Atoms in electric fields: the

Stark effect
What happens if we place an atom in a uniform electric field? One observes

a splitting and shifting of energy levels (spectral lines). This was first dis-
covered by Johannes Stark in 1913, i.e. in the same year, in which Bohr
developed his model of the hydrogen atom. Later on, this problem was one
of the first treated by Schrödinger shortly after the discovery of his wave
equation. Schrödinger used perturbation theory, and this is what we will do
in this chapter.
The first step is to figure out what kind of modification a classical electric
field brings about. Let’s assume the field E is oriented in positive z-direction:
E = F k̂ (2.1)
The associated electrostatic potential reads
Φ(r) = −E · r = −F z (2.2)
֒→ potential energy of an electron
W (r) = −eΦ(r) = eF z (2.3)
has to be added to the Hamiltonian. The task then is to solve
Ĥ|ϕα i = Eα |ϕα i (2.4)
for (using atomic units from now on)
1 1
Ĥ = − ∇2 − + F z (2.5)
2 r
16
17
Taking a look at the total potential (Coulomb + Stark) one finds that
tunnelling is possible — i.e. in a strict sense the Hamiltonian (2.5) does not
support stationary states. Eventually, a bound electron will tunnel through
the barrier and escape from the atom. In practice, however, the Stark po-
tential is weak compared to the Coulomb potential and the tunnel effect is
unimportant unless one studies highly-excited states. This is why we can
apply stationary perturbation theory (PT).
2.1 Stationary perturbation theory for non-

degenerate systems
a) General formalism
Task: solve stationary SE
Ĥ|ϕα i = Eα |ϕα i (2.6)
decompose
Ĥ = Ĥ0 + Ŵ (2.7)
and assume that the eigenvalue problem of Ĥ0 is known
Ĥ0 |ϕ0α i = Eα(0) |ϕ0α i, hϕ0α |ϕ0β i = δαβ (2.8)
We seek solutions of. Eq. (2.6) in terms of a Taylor (like) expansion based on
the (nondegenerate) eigenvalues and eigenstates of the ’unperturbed problem’
Eq. (2.8). Therefore, we require that the ’perturbation’ Ŵ be small. Let’s
introduce a smallness parameter λ:
Ŵ ≡ λŵ with λ ≪ 1 (2.9)

(2.6)

−→ Ĥ0 + λŵ |ϕα (λ)i = Eα (λ)|ϕα (λ)i (2.10)
Taylor expansions about λ = 0:

dEα (λ) 1 d2 Eα (λ)
Eα (λ) = Eα(0)
+ λ+ λ2 + . . . (2.11)
dλ λ=0 2 dλ2 λ=0
d
|ϕα (λ)i = |ϕ0α i + |ϕα (λ)i|λ=0 λ + . . . (2.12)
dλ
18
We need to find expressions for the derivatives in Eqs. (2.11), (2.12):

consider derivative of. Eq. (2.10):
d
Ĥ0 + λŵ − Eα (λ) |ϕα (λ)i = 0
dλ
⇐⇒ Ĥ0 + λŵ − Eα (λ) |ϕ′α (λ)i + ŵ − Eα′ (λ) |ϕα (λ)i = 0
dEα
(Eα′ = etc.)
dλ
֒→ hϕβ (λ)|Ĥ(λ) − Eα (λ)|ϕ′α (λ)i + hϕβ (λ)|ŵ − Eα′ (λ)|ϕα (λ)i = 0
i) α = β
=⇒ Eα′ (λ) = hϕα (λ)|ŵ|ϕα (λ)i (2.13)
ii) α 6= β
hϕβ (λ)|ŵ|ϕα (λ)i

=⇒ hϕβ (λ)|ϕ′α (λ)i = (2.14)
Eα (λ) − Eβ (λ)
′
In order
to use
Eq. (2.14) for an expansion of |ϕα i in terms of the orthonormal
basis |ϕα i we have to consider the coefficient hϕα (λ)|ϕ′α (λ)i in addition.
If we assume that hϕα (λ)|ϕ′α(λ)i = hϕ′α (λ)|ϕα (λ)i (i.e. we choose real states
which is not a restriction) we can show that
hϕα (λ)|ϕ′α (λ)i = 0
d
proof : hϕα (λ)|ϕα (λ)i = hϕ′α (λ)|ϕα (λ)i + hϕα (λ)|ϕ′α (λ)i
dλ | {z }
=1
= 2hϕα (λ)|ϕ′α(λ)i = 0
X
֒→ |ϕ′α (λ)i = |ϕβ (λ)ihϕβ (λ)|ϕ′α (λ)i
β
X hϕβ (λ)|ŵ|ϕα (λ)i
= |ϕβ (λ)i (2.15)
β6=α
19
Let’s also consider the 2nd derivative term in Eq. (2.11):

d2 d ′ (2.13) d
Eα (λ) = Eα (λ) = hϕα (λ)|ŵ|ϕα (λ)i
dλ2 dλ dλ
= hϕ′α (λ)|ŵ|ϕα (λ)i + hϕα (λ)|ŵ|ϕ′α (λ)i
(2.15) X |hϕα (λ)|ŵ|ϕβ (λ)i|2
= 2 (2.16)
β6=α
Higher order terms can be calculated by differentiating expressions (2.15),

(2.16) successively. We stop here and insert (2.13)–(2.16) in the Taylor ex-
pansions (2.11), (2.12):
Eα (λ) = Eα(0) + λhϕα (0)|ŵ|ϕα (0)i

X |hϕα (0)|ŵ|ϕβ (0)i|2
+ λ2 + ...
β6=α
E α (0) − Eβ (0)
X |hϕ0α|Ŵ |ϕ0β i|2

= Eα(0) + hϕ0α |Ŵ |ϕ0α i + (0) (0)
+ . . . (2.17)
β6=α Eα − Eβ
X hϕ0β |Ŵ |ϕ0α i
|ϕα (λ)i = |ϕ0α i + (0) (0)
|ϕ0β i + . . . (2.18)
β6=α Eα − Eβ
Eqs. (2.17), (2.18) are the standard expressions for the lowest-order correc-
tions — the glorious result of this section!
Remarks:
(0) (0)
1. Derivation and result are valid only if Eα 6= Eβ (i.e. no degeneracies)
2. Convergence of perturbation series?
This cannot be answered in general. In some cases, perturbation ex-
pansions do converge, in some they do not, and in some other cases the
perturbation series turns out to be a so-called semi-convergent (asymp-
totic) series.
Consistency criterion for convergence (cf. Eq. (2.18))

hϕ0 |Ŵ |ϕ0 i
β α
(0) (0) ≪1, (for α 6= β)
Eα − E
β
20
3. In practice, ’exact’ calculations beyond 1st order in the energy are often
not feasible due to (infinite) sums over all basis states (cf. Eq. (2.17)).
4. Literature: [Gri], Chap. 6.1; [Lib], Chap. 13.1
b) Application to H(1s) in an electric field

Ingredients (in atomic units):
1
ϕ01s (r) = √ e−r
π
(0)
E1s = −0.5 a.u.
W = Fz
1st -order energy correction:

(1)
∆E1s = hϕ01s |W |ϕ01s i (2.19)
Z
F
= e−2r r cos θd3 r
π
Z Z 1 Z 2π
F ∞ 3 −2r
= r e dr cos θd cos θ dϕ
π 0 −1 0
Z ∞ 1

= F r 3 e−2r drx2 = 0 (2.20)
0 −1
(with x = cos θ)
The 2nd -order energy correction
(2)
X |hϕ01s |F z|ϕ0β i|2
∆E1s = (0) (0)
β6=1s E1s − Eβ
is hard to calculate due to the infinite sum (which actually also involves
an integral over the continuum states). Let us content ourselves with an
estimate.
(0) (0) (2)
Note that E1s − Eβ < 0, i.e., ∆E1s < 0.
21
Consider
(2)
X |hϕ01s |z|ϕ0β i|2 F2 X
2
|∆E1s | = F (0) (0)
< (0) (0)
hϕ01s |z|ϕ0β ihϕ0β |z|ϕ01s i
β6=1s Eβ − E1s En=2 − E1s β6=1s
!
F2 X
= (0) (0)
hϕ01s |z |ϕ0β ihϕ0β |z|ϕ01s i − hϕ01s |z|ϕ01s ihϕ01s |z|ϕ01s i
En=2 − E1s β
2 2
8F (2.20) 8F
= (hϕ01s |z 2 |ϕ01s i − hϕ01s |z|ϕ01s i2 ) = hϕ01s |z 2 |ϕ01s i
3 3
One finds hϕ01s |z 2 |ϕ01s i = 1 and obtains
(2) 8
|∆E1s | < F 2 quadratic Stark effect (2.21)
3
The exact result (see [Sha], Chap. 17) is
(2) 9
∆E1s = − F 2 (2.22)
4
Interpretation:
Consider a classical charge distribution ρ in an electric field. The associated
potential energy is
Z Z
W = ρ(r)Φ(r)d r = −F ρ(r)zd3 r
3
= −F dz
where dz is the z-component of the dipole moment.

Link this to QM by recognizing that ρ(r) = −|ϕ(r)|2 (atomic units!).
Z
֒→ dz = − |ϕ1s (r)|2 zd3 r = −hϕ1s |z|ϕ1s i
Now use Eq. (2.18) to obtain

X |hϕ01s |z|ϕ0β i|2 2 (2) 16
dz = −2F (0) (0)
+ O(λ2 ) ≈ − ∆E1s < F
β6=1s E1s − Eβ F 3
22
Summary:
(1)
• ∆E1s = 0 expresses the fact that the unperturbed hydrogen ground
(0)
state has no static dipole moment dz (this is in fact true for any
spherically symmetric charge distribution).
(2)
• ∆E1s 6= 0 expresses the fact that it has a nonzero induced dipole
(1) (1)
moment dz , i.e., a nonzero dipole polarizability αD := dz /F . We
have found αD < 16/3 a.u. (the exact result being αD = 9/2 a.u. )
2.2 Degenerate perturbation theory

Problem:
Ĥ = Ĥ0 + λŵ (2.23)
with
Ĥ0 |ϕ0αj i = Eα(0) |ϕ0αj i, j = 1, . . . , gα (2.24)
where gα is the degeneracy level. The set {|ϕ0αj i, j = 1, . . . , gα } spans a gα -
(0)
dimensional subspace of Hilbert space associated with the eigenvalue Eα .
This implies that any linear combination of these states is an eigenstate of Ĥ0
(0)
for Eα . When the perturbation is turned on, the degeneracy is (normally)
lifted:
Ĥ|ϕαj i = Eαj |ϕαj i. (2.25)
The question arises which of the degenrate states is approached by a given
state |ϕαj i in the limit λ → 0. At this point we can’t say more than that it
can be any linear combination, i.e.
gα
λ→0
X
|ϕαj i −→ |ϕ̃0αj i = aαkj |ϕ0αk i. (2.26)
k=1
The unknown states |ϕ̃0αj i are the 0th -order states of the pertubation expan-
sion:
(1)
Eαj = Eα(0) + λEαj + · · · (2.27)
|ϕαj i = |ϕ̃0αj i + λ|ϕ1αj i + · · · (2.28)
23
Note that this expansion is of the same type as the previous Taylor series of
Eqs. (2.11), (2.12) if one identifies

(1) (1) dEα (λ)
∆Eα = λEα = λ etc.
dλ λ=0
Now proceed as follows: Insert (2.27), (2.28) into the Schrödinger equation
(2.25) to obtain

(Ĥ0 + λŵ) |ϕ̃0αj i + λ|ϕ1αj i + · · ·
(1)
= (Eα(0) + λEαj + · · · ) |ϕ̃0αj i + λ|ϕ1αj i + · · · ,
sort this in terms of powers of λ
λ0 : Ĥ0 |ϕ̃0αj i = Eα(0) |ϕ̃0αj i
(1)
λ1 : Ĥ0 |ϕ1αj i + ŵ|ϕ̃0αj i = Eα(0) |ϕ1αj i + Eαj |ϕ̃0αj i,
and project the second equation onto an undisturbed eigenstate of the same
subspace:
(1)
0 = hϕ0αl |Ĥ0 − Eα(0) |ϕ1αj i + hϕ0αl |ŵ − Eαj |ϕ̃0αj i
(1)
⇔ 0 = hϕ0αl |ŵ − Eαj |ϕ̃0αj i
gα
X (1)
⇔ 0 = hϕ0αl |ŵ − Eαj |ϕ0αk iaαkj l = 1, . . . , gα (2.29)
k=1
Eq. (2.29) is a standard matrix eigenvalue problem of size gα × gα . Its solu-

tion is what (lowest-order) degenerate perturbation theory boils down to in
practice. Here is how to do it:
(1)
(i) Solve secular (characteristic) equation det(wα − Eα 1) = 0 → obtain
(1)
eigenvalues {Eαj , j = 1, . . . , gα}, which happen to be the first-order
energy corrections, i.e. the quantities we are after!
(ii) Find mixing coefficients {aαkj , k, j = 1, . . . , gα } by inserting eigenvalues
into the matrix equations (2.29).
(1)
(ii) Check that hϕ̃0αl |ŵ|ϕ̃0αk i = Eαj δlk (i.e. perturbation matrix is diagonal
with respect to the states {|ϕ̃0αk i}).
Note that higher-order calculations are possible, but tedious and not dis-
cussed in our textbooks. Refs. [Gri], Chap. 6.2 and [Lib], Chap. 13.2, (13.3)
merely paraphrase the material provided in this section.
24
2.3 Electric field effects on excited states: the

linear Stark effect
Let us now apply degenerate perturbation theory to the problem of the ex-
cited hydrogen states in a uniform electric field. To this end we have to set
up and diagonalize the perturbation matrix. Let’s first look at
a) Matrix elements and selection rules
α explicitly 0
wlk = hϕ0αl |ŵ|ϕ0αk i −→ hϕnlm|z|ϕ0nl′ m′ i
with (cf. Eq. (1.22))
λ ≡ F (smallness parameter)
ϕnlm (r) = Rnl (r)Ylm (Ω)
r
4π
z = r cos θ = rY10 (Ω)
3
r Z ∞ Z
0 0 4π 3 ∗
֒→ hϕnlm |z|ϕnl′ m′ i = r Rnl (r)Rnl′ (r)dr Ylm (Ω)Y10 (Ω)Yl′ m′ (Ω)dΩ
3 0
The angular integral is a special case of a more general integral over three (ar-
bitrary) spherical harmonics, the result of which is known (”Wigner-Eckart
theorem”):
r Z
4π ∗
Ylm (Ω)YLM (Ω)Yl′ m′ (Ω)dΩ
2L + 1

m
p
′ l L l′ l L l′
= (−1) (2l + 1)(2l + 1) (2.30)
−m M m′ 0 0 0
with
j1 j2 j3
∈R ”Wigner’s 3j-symbol”
m1 m2 m3
The 3j-symbols are closely related to the Clebsch-Gordan coefficients. We
don’t need to know much detail here other than that they fulfill certain
selection rules, i.e., they are zero in many cases:
25

j1 j2 j3
6= 0 iff m1 + m2 + m3 = 0 ∧ |j1 − j2 | ≤ j3 ≤ j1 + j2
m1 m2 m3

j1 j2 j3
6 = 0 iff j1 + j2 + j3 = even ∧ |j1 − j2 | ≤ j3 ≤ j1 + j2
0 0 0
These relations imply that Eq. (2.30) is nonzero only if
m = m′ and ∆l = l − l′ = ±1 (2.31)
These conditions are called electric dipole selection rules.

Literature on angular momentum, Clebsch-Gordan coefficients, and 3j-symbols:
[Lib], Chap. 9; [Mes], Vol II, Chap. 13 (and appendix); [CT], Chaps. 6, 10
(and complements)
b) Linear Stark effect for H(n = 2)

Let’s do an explicit calculation for the four degenerate states of the hydrogen
L shell: {ϕ02s , ϕ02p0 ϕ02p−1 ϕ02p+1 }
• matrix elements:
due to the dipole selection rules (2.31) there is only one nonzero matrix
element we need to calculate:
Z ∞ Z 1 Z 2π
0 0 1 4 −r 2
w12 = hϕ2s |r cos θ|ϕ2p0 i = (2 − r)r e dr cos θ d cos θ dϕ
32π 0 −1 0
Z ∞ Z ∞
1 4 −r 5 −r 1
= 2 r e dr − r e dr = (2 × 4! − 5!) = −3 (a.u.)
24 0 0 24
= w21
→ perturbation matrix:
 
0 w12 0 0
 w12 0 0 0 
w=
 0

0 0 0 
0 0 0 0
26
• secular equation:
 
−E (1) w12 0 0
 w12 −E (1) 0 0 
det 
 0 (1)
 = 0 (2.32)
0 −E 0 
0 0 0 −E (1)
⇔ (E (1) )4 − (E (1) )2 w12
2
= 0
(1)
֒→ E = {0, 0, w12, −w12 }
• mixing coefficients
(1)
(i) E1,2 = 0:
   (1,2)   
0 w12 0 0 a2s 0
 (1,2) 
 w12 0 0 0 
 a2p0   0 
  =  
0   a(1,2)
 0 
0 0 2p−1   0 
0 0 0 0 (1,2)
a2p+1 0
(1,2) (1,2)
⇔ a2s = a2p0 = 0
(1,2) (1,2)
֒→ |ϕ̃0E (1) i = a2p−1 |ϕ02p−1 i + a2p+1 |ϕ02p+1 i
1,2
We can choose the nonzero coefficients as we please — so let’s pick
|ϕ̃0E (1) i ≡ |ϕ02p−1 i

1
|ϕ̃0E (1) i ≡ |ϕ02p+1 i

2
(1)
(ii) E3 = w12 :
   (3)   
−w12 w12 0 0 a2s 0
 (3) 
 w12 −w12 0 0 
 a2p0   0 
  =  
0   a(3)
 0 
0 0 2p−1   0 
0 0 0 0 (3)
a2p+1 0
(3) (3) (3) (3)
⇔ a2s = a2p0 , a2p−1 = a2p+1 = 0
27
(1)
(iii) E4 = −w12 :
   (4)  
w12 w12 0 0 a2s 0
 (4) 
 w12 w12 0 0 
 a2p0   0 
  =  
0 0   a(4)
 0 
0 2p−1   0 
0 0 0 0 (4)
a2p+1 0
(4) (4) (4) (4)
⇔ a2s = −a2p0 , a2p−1 = a2p+1 = 0
֒→ normalized ’Stark’ states:

1
|ϕ̃0E (1) i = √ |ϕ02s i + |ϕ02p0 i (2.33)
3 2
1
|ϕ̃0E (1) i = √ |ϕ02s i − |ϕ02p0 i (2.34)
4 2
Summary
1. The (weak) electric field results in a splitting of the energy level — the
degeneracy is (partly) lifted. The energy shifts are linear in the electric
field strength:
(1)
∆E1,2 = 0
(1)
∆E3 = λw12 = −3F
(1)
∆E4 = −λw12 = 3F
2. Note that the ’original’ L-shell states have no static dipole moment
since
hϕ0nlm |z|ϕ0nlm i = 0
3. The Stark states (2.33), (2.34) do have nonzero static dipole moments
(calculate them!). Check the Maple worksheet starkstates.mw to see
how these states look like.
4. Cylindrical symmetry is preserved by the Stark potential W = F z,

since
[ˆlz , W ] = 0,
i.e., m is still a good quantum number, but l is not.
28
5. The diagonalization procedure can be simplified by recognizing that the

perturbation matrix is of block-diagonal structure (with three blocks
corresponding to the magnetic quantum numbers m = 0, m = −1, m =
+1. Consider three blocks Ai :
 
A1 0 0
det  0 A2 0  = 0
0 0 A3
֒→ detA = 0 ⇔ detAi = 0 for i = 1, . . . , 3
The only nontrivial secular equation for the L-shell problem then is (cf.
Eq. (2.32)):

−E (1) w12
det = 0
w12 −E (1)
In a similar fashion, one can study the Stark problem for the nine
M shell states. The perturbation matrix can be decomposed into five
blocks corresponding to the states with magnetic quantum numbers
m = −2 to m = 2.
Chapter 3
Interaction of atoms with

radiation
The first question to be addressed when discussing the interaction of atoms

with radiation concerns the level on which the electromagnetic (EM) field
shall be described. It seems natural to aim at a quantum theory. It is only
on this level that photons come into the picture. We will take a look at them
a bit later, but start off with coupling the classical EM field to our quantal
description of the (hydrogen) atom. It turns out that this is sufficient for the
description of a number of processes including the photoelectric effect, which
prompted Einstein to introduce the notion of photons in the first place.
3.1 The semiclassical Hamiltonian

The goal is to derive a Hamiltonian, which accounts for the interaction of an
atom with a classical EM field. Let’s start completely classically.
a) Classical particle in an EM field
• The action of a classical EM field on a classical particle is described by
the Lorentzian force

FL = q E + (v × B)
where q and v are the charge and the velocity of the particle and E and
B the electric and magnetic fields. However, if we want to construct a
Hamiltonian we need EM potentials instead of EM fields:
29
30
• EM potentials
the scalar potential Φ and the vector potential A are defined via
B = ∇×A (3.1)
∂A
E = −∇Φ − (3.2)
∂t

∂A
֒→ FL = q −∇Φ − + (v × (∇ × A)) (3.3)
∂t
this equation can be rewritten by introducing a generalized (i.e., velocity-
dependent) potential energy:
• Generalized potential energy
U := q(Φ − A · v) (3.4)
one can show that Eq. (3.3) can be written as
d
FL = −∇U + ∇v U (3.5)
dt
i.e.,
∂U d ∂U
FLi = − − i = 1, 2, 3
∂xi dt ∂ ẋi
the generalized potential paves the way to set up the Lagrangian:
• Lagrangian
m 2
L= T −U = v − qΦ + qA · v (3.6)
2
if one works out the Lagrangian equations of motion one finds ma = FL ,
i.e., Newton’s equation of motion with the Lorentzian force. This shows
that the construction is consistent. Now we are only one step away from
the Hamiltonian:
• Hamiltonian
H =p·v−L (3.7)
31
with the generalized momentum
p = ∇v L = mv + qA (3.8)
1
v = (p − qA) (3.9)
m
if one uses Eq. (3.9) in Eq. (3.7) one arrives at
1
H= (p − qA)2 + qΦ (3.10)
2m
for details see [GPS], Chaps. 1.5 and 8.1
b) Quantum mechanical Hamiltonian for an electron
• add a scalar potential V (to account, e.g., for the Coulomb potential
of the atomic nucleus)
• q = −e
• quantization: p → p̂ = −i~∇
1
֒→ Ĥ = (p̂ + eA)2 − eΦ + V
2m
1
= (−~2 ∇2 − i~e∇ · A(r, t) − i~eA(r, t) · ∇ + e2 A2 (r, t))
2m
− eΦ(r, t) + V (r)
~2 2 e~ e~
= − ∇ + V (r) + A(r, t) · ∇ + (∇ · A(r, t))
2m mi 2mi
e2 2
+ A (r, t) − eΦ(r, t)
2m
≡ Ĥ0 + Ŵ (t) (3.11)
question: how do A and Φ look like?

֒→ assume EM field without sources (neither charges nor currents). The
homogeneous Maxwell equations for A and Φ take a simple form if one uses
32
the so-called Coulomb gauge defined by the requirement ∇ · A = 0. One is

then left with
1 ∂2
∇2 A − A = 0 (3.12)
c2 ∂t2
∇2 Φ = 0 (3.13)
The only solution to Eq. (3.13) which is compatible with the requirement
that free EM waves are transverse is the trivial one Φ = 0. A monochromatic
(real) solution of Eq. (3.12) reads
A(r, t) = π̂|A0 | cos(k · r − ωt + α) (3.14)
with the unit vector π̂ being orthogonal to the wave vector k. This ensures
that indeed ∇ · A = 0. If one inserts (3.14) into (3.12) one obtains the
dispersion relation ω = ck. For details on the solutions of the free Maxwell
equations see [Jac], Chap 6.5.
Using the gauge conditions we arrive at the perturbation
e e2 2
Ŵ (t) = A(t) · p̂ + A (3.15)
m 2m
For weak fields one can neglect the A2 term. Ŵ = me A · p̂ is the usual
starting point for a perturbative treatment of atom-radiation interactions in
the semiclassical framework. The perturbation depends on time. We need a
time-dependent version of perturbation theory to deal with it.
3.2 Time-dependent perturbation theory

a) General formulation
The Hamiltonian under discussion is of the generic form
Ĥ(t) = Ĥ0 + Ŵ (t)

≡ Ĥ0 + λŵ(t) (3.16)
task: solve the time-dependent Schrödinger equation (TDSE)
i~∂t |ψ(t)i = Ĥ(t)|ψ(t)i (3.17)

33
assume that Ŵ (t ≤ t0 ) = 0
֒→ t ≤ t0 : Ĥ0 |ϕj i = ǫj |ϕj i j = 0, 1, . . .
assume |ψ(t0 )i = |ϕ0 i , (initial state) (3.18)
X i
ansatz : |ψ(t)i = cj (t)e− ~ ǫj t |ϕj i (3.19)
j
X
= cj (t)|ψj (t)i (3.20)
j
insertion of Eq. (3.19) into Eq. (3.17):

X i X i
֒→ i~ċj + ǫj e− ~ ǫj t |ϕj i = cj e− ~ ǫj t Ĥ(t)|ϕj i | hψk (t)|
j j
X i
֒→ i~ċk = λ e ~ (ǫk −ǫj )t cj hϕk |ŵ(t)|ϕj i (3.21)
j
’coupled-channel’ equations. (still exact if basis is complete)
If Ŵ (t > T ) = 0 ֒→ ck (t > T ) = const and

2 2 2
pk = |ck | = |hψk |ψi| = |hϕk |ψi| = const (3.22)
t>T t>T t>T
֒→ transition probabilities ϕ0 −→ ϕk
note that X X
pk = hψ|ϕk ihϕk |ψi = hψ|ψi = 1
k k
as it should.
Ansatz for solution of Eq. (3.21): power series expansion
(0) (1) (2)
ck (t) = ck (t) + λck (t) + λ2 ck (t) + . . . (3.23)
insertion into Eq. (3.21) yields

(0) (1) 2 (2)
i~ ċk + λċk + λ ċk + . . .
X (0) (1) (2)
i
=λ cj + λcj + λ2 cj + . . . e ~ (ǫk −ǫj )t hϕk |ŵ(t)|ϕj i
j
34
֒→
(0)
λ0 : i~ċk = 0
(1)
X (0) i
λ1 : i~ċk = cj e ~ (ǫk −ǫj )t hϕk |ŵ(t)|ϕj i
j
(2)
X (1) i
2
λ : i~ċk = cj e ~ (ǫk −ǫj )t hϕk |ŵ(t)|ϕj i
j
these equation can be solved successively:

(0)
λ0 : ck (t) = const = δk0 (cf. Eq. (3.18)) (3.24)
(1)
X i
λ1 : i~ċk = δj0 e ~ (ǫk −ǫj )t hϕk |ŵ(t)|ϕj i
j
i
= e ~ (ǫk −ǫ0 )t hϕk |ŵ(t)|ϕ0 i
Z t
(1) (1) i i ′
֒→ ck (t) − ck (t0 )
= − e ~ (ǫk −ǫ0 )t hϕk |ŵ(t′ )|ϕ0 i dt′ (3.25)
| {z } ~ t0
=0
(as λ = 0 at t = t0 )
accordingly:
Z Z ′
2 (2) 1 X t ′ t ′′ i (ǫk −ǫj )t′ i (ǫj −ǫ0 )t′′
λ : ck (t) =− 2 dt dt e ~ e~
~ j t0 t0
× hϕk |ŵ(t′ )|ϕj ihϕj |ŵ(t′′ )|ϕ0 i (3.26)

Comments:
(i) ”exact” calculations beyond 1st order are in general impossible due to
infinite sums
(ii) interpretation
t0 t
st Ŵ
1 order |ϕ0 i −→ |ϕk i ’direct transition’
nd Ŵ Ŵ
2 order |ϕ0 i −→ |ϕj i −→ |ϕk i
transition via ’virtual’ intermediate states (two steps)
(iii) further reading (and better visualization in terms of generic diagrams):
[Mes] II, Chap. 17
35
b) Discussion of the 1st -order result

To 1st order time-dependent perturbation theory we have (cf. Eqs. (3.24)
and (3.25)): Z
i t iωk0 t′
ck (t) ≈ δk0 − e Wk0 (t′ ) dt′ (3.27)
~ t0
ǫk − ǫ0
with ωk0 = ωk − ω0 =
~
transition frequency
Wk0 = hϕk |Ŵ |ϕ0 i = λhϕk |ŵ|ϕ0 i
transition
Z t matrix element
1 ′
p0→k = 2| eiωk0 t Wk0 (t′ ) dt′ |2
~ t0
transition probability
What about the ’elastic channel’ (k = 0)?

the calculation of the probability that the system remains in the initial state
is a bit trickier due to the occurrence of the ’1’ in c0 . To be consistent in the
orders of the smallness parameter λ one has to consider
(0) (1) (2)
p0→0 = |c0 + λc0 + λ2 c0 + . . . |2
(1) (1)∗ (2) (2)∗ (1)
= 1 + λ(c0 + c0 ) + λ2 (c0 + c0 + |c0 |2 ) + O(λ3)
(2) (1)
= 1 + λ2 (2Re(c0 ) + |c0 |2 ) + O(λ3 )
X
= ... = 1 − p0→k (3.28)
k6=0
the latter result can be worked out explicitly and is not surprising: it ex-
presses probability conservation.
36
Examples
(i) Slowly varying perturbation
Let’s assume that the perturbation is turned on very gently after t = t0 .
It might then stay constant for a while and/or is turned off equally
gently. This is to say that the time derivative of Ŵ is a very small
quantity for all times.
k 6= 0
Z
i t iωk0 t′
֒→ ck (t) = − e Wk0 (t′ ) dt′
~ t0
t Z t
i h 1 iωk0 t′ ′ 1 iωk0 t′ ′ ′
i
= − e Wk0 (t ) − e Ẇk0 (t ) dt
~ iωk0 t0 iωk0 t0
Ẇk0 ≈0 hϕk |Ŵ (t)|ϕ0 i iωk0 t
= − e
ǫk − ǫ0
let’s plug this into the time-dependent state vector:

X i
|ψ(t)i = ck (t)e− ~ ǫk t |ϕk i
k
i
X hϕk |Ŵ (t)|ϕ0 i i
= c0 (t)e− ~ ǫ0 t |ϕ0 i + e− ~ ǫ0 t |ϕk i
k6=0
ǫ0 − ǫk
the amplitude c0 can be set equal to 1. This introduces at most a small

phase error (up to first order)
X hϕk |Ŵ (t)|ϕ0 i i
֒→ |ψ(t)i = |ϕ0 i + |ϕk i e− ~ ǫ0 t
k6=0
ǫ0 − ǫk
i
≡ |ϕ0 (t)ie− ~ ǫ0 t (3.29)
comparing this to the general results of stationary PT one can interpret

|ϕ0 (t)i as the first-order eigenstate of Ĥ(t) = Ĥ0 + Ŵ (t) with eigenen-
(1)
ergy ǫ0 (t) = ǫ0 + hϕ0 |Ŵ (t)|ϕ0 i. The system is in the ground state
of the instantaneous Hamiltonian Ĥ(t) at all times. This situation is
called adiabatic.
37
Comments:
(i) The argument can be generalized to strong perturbations. The
general adiabatic approximation then results in the statement: if
the perturbation varies slowly with time, the system is found in
an eigenstate of Ĥ(t) at all times.
(ii) Adiabatic conditions are realized, e.g., if atom beams are directed
through slowly varying magnetic fields (→ Stern-Gerlach experi-
ment) and in slow atomic collisions. In the latter case the electrons
adapt to the slowly varying Coulomb potentials of the (classically)
moving nuclei and do not undergo transitions. They are in so-
called quasimolecular states during the collision and back in their
initial atomic states thereafter.
(iii) further reading: [Boh], Chap. 20; [Gri], Chap. 10
(ii) Sudden perturbation
V 
 0 t ≤ t0 ≡ 0
Ŵ (t) =

Ŵ t > t0
t
k 6= 0
Z
i t iωk0 t′
֒→ ck (t) = − e Wk0 (t′ ) dt′
~ 0
Z
hϕk |Ŵ |ϕ0 i t iωk0 t′ ′
= e dt
i~ 0
hϕk |Ŵ |ϕ0 i iωk0 t
= − e −1
~ωk0
֒→ transition probability
4|Wk0|2
p0→k (t) = |ck (t)|2 = f (t, ωk0) (3.30)
~2
sin2 ωk0
2
t
ωk0 →0 t
2
f (t, ωk0) = 2
−→ (3.31)
ωk0 4
38
Figure 3.1: y = f (t, ωk0)
Significant transitions occur only around ωk0 = 0 within the width

∆ω = 2πt . This is a manifestation of the energy-time uncertainty rela-
tion: if one waits long enough, transitions can only occur into states
that have the same energy as the initial state. One can state this more
precisely (mathematically) by considering the limit t −→ ∞:
t→∞ πt
f (t, ωk0) −→ δ(ωk − ω0 ) (3.32)
2
2πtt→∞
֒→ p0→k |Wk0|2 δ(ωk − ω0 )
−→
~
The sudden perturbation sounds academic, but it has an important
application (see later).
(iii) Periodic perturbation


 0 t ≤ t0 = 0
Ŵ (t) = (3.33)
 iωt † −iωt
B̂e + B̂ e t > t0
39
(note that Ŵ = Ŵ † )
Z t
1 ′
֒→ ck (t) = eiωk0 t Wk0 (t′ ) dt′
i~ 0
(
1 hϕk |B̂|ϕ0 i i(ωk0 +ω)t
= − e −1
~ ωk0 + ω
)
hϕk |B̂ † |ϕ0 i i(ωk0 −ω)t
+ e −1
ωk0 − ω
2π
if t ≫ ω
(i.e. ∆ω ≪ ω):
4|Bk0 |2 n o
p0→k (t) = f (t, ω k0 + ω) + f (t, ω k0 − ω) (3.34)
~2
2πt n o
t→∞ 2
−→ |Bk0| δ(ωk − ω0 + ω) + δ(ωk − ω0 − ω)
~
with Bk0 = hϕk |B̂|ϕ0 i and Eq. (3.31)
Comments:
(i) ’Resonances’ at ωk0 = ±ω: significant transitions occur only around

these frequencies
• ωk0 = −ω ⇐⇒ ǫk = ǫ0 − ~ω
e 0
stimulated emission (of energy)
h w
(only possible if ϕ0 is not the ground state)
e k
• ωk0 = +ω ⇐⇒ ǫk = ǫ0 + ~ω
e k
absorbtion (of energy)
h w
e 0
(ii) Since ϕ0 is not the ground state in the case of stimulated emission
it makes sense to change the notation and use ϕi for the initial
and ϕf for the final state. Transition frequencies are then denoted
as ωf i etc.
40
(iii) We were careful enough to write that energy is emitted or absorbed

if the resonance conditions are met. We can’t tell in which form
this happens. Later we will see that the energy is carried by
photons if the perturbation is exerted on the atom by the quantized
radiation field. The perturbation derived in Sec. 3.1 corresponds
to a classical radiation field. Let’s stick to this case first and
convince ourselves that it can be written in the form (3.33).
(iv) Connection to atom-radiation interaction
In Sec. 3.1 we found that for weak EM fields the perturbation
takes the form
e
Ŵ = A · p̂ (3.35)
m
If we use Eq. (3.14) for a monochromatic field we obtain
e
Ŵ = A0 ei(k·r−ωt) π̂ · p̂ + A∗0 e−i(k·r−ωt) π̂ · p̂
2m
= B̂eiωt + B̂ † e−iωt
with
e ∗ −ik·r
B̂ = A e π̂ · p̂ (3.36)
2m 0
(v) Validity of first-order time-dependent perturbation theory
We have two conditions to fulfill to be able to apply our results
for the periodic perturbation:
• criterion to avoid overlap of the resonances
2π 2π
∆ω = ≪ω ⇔ t≫
t ω
• validity criterion on resonance
4|Bf i |2 |Bf i |2 2
pi→f = f (t, ω f i ± ω = 0) = t ≪1
~2 ~2
~
⇔ t ≪
|Bf i |
combine 2π 2π ~
−→ = ≪
ω |ωf i | |Bf i |
⇔ |∆ǫf i | ≫ |Bf i |
41
3.3 Photoionization
Let us elaborate on the case of absorption. If the energy, i.e., the field
frequency ω is high enough, the atom will be ionized. The final state of the
electron will then be a continuum state and this requires some additional
considerations, since such a state is not normalizable. This implies that
pi→f = |hϕf ||ψ(t)i|2 is a probability density rather than a probability. A
proper probability is obtained if one integrates over an interval of final states
a) Transitions into the continuum1 .
e k+ D e Z ǫf +∆ǫ
e k-D e
Pi→f := pi→f (ǫf ′ )ρ(ǫf ′ ) dǫf ′ (3.37)
ǫf −∆ǫ
e 0
with ρ(ǫf ′ ): density of states in interval [ǫf − ∆ǫ; ǫf + ∆ǫ]
Let’s be a bit more specific and calculate the density of states for free-particle
continuum states
1 i
ϕf (r) = hr|pi = exp( p · r)
[2π~]3/2 ~
These states are ’normalized’ with respect to δ-functions:

Z Z
3 1 i ′
′ ′
hp|p i = hp|rihr|p i d r = 3/2
exp[ (p − p) · r]d3 r = δ(p′ − p)
[2π~] ~
Nevertheless, they fulfill a completeness relation (like the position eigenstates

|ri) such that for any (normalized) state |ψi
Z Z
1 = hψ|ψi = hψ|pihp|ψi d p = |ψ(p)|2 d3 p
3
and the density of states with respect to momentum is simply ρ(p) = 1. We

need to transform this from momentum to energy. For free particles we have
1
Unfortunately, the figure doesn’t correspond to the i → f notation, but I cannot
change it easily!
42
the simple relation ǫf = p2 /2m such that
dp
֒→ d3 p = p2 dpdΩp = p2 dǫf dΩp
dǫf
p
= 2m3 ǫf dǫf dΩp
Z Z p Z
2 3 3 2
֒→ 1 = |ψ(p)| d p = 2m ǫf |ψ(p)| dΩp dǫf
Z
= ρ(ǫf )pi→f (ǫf )dǫf
with p
ρ(ǫf ) = 2m3 ǫf
Let’s go back to the probability (3.37) and insert the first-order result
(3.34):
Z ǫf +∆ǫ n o
4
Pi→f = 2 |Bf ′ i |2 ρ(ǫf ′ ) f (t, ωf ′ i + ω) + f (t, ωf ′ i − ω) dǫf ′
~ ǫf −∆ǫ
Z ǫf +∆ǫ
abs 4 2
Pi→f ≈ 2 |Bf i | ρ(ǫf ) f (t, ωf ′ i − ω)dǫf ′
~ ǫf −∆ǫ
Z ∞
4 2 sin2 ( ω̃t
2
)
≈ |Bf i | ρ(ǫf ) dω̃
~ −∞ ω̃ 2
2π
= |Bf i |2 ρ(ǫf )t
~
R ∞ sin2 ( ω̃t )
where we have used −∞ ω̃2 2 dω̃ = πt 2
. A similar result is obtained for the
case of emission. One defines a transition rate wi→f = dtd Pi→f to obtain
Fermi’s Golden Rule (FGR)
2π
e,a
|Bf i |2 ρ(ǫf )

wi−→ f = (3.38)
~ ǫf =ǫi ±~ω
43
b) Dipole approximation
In a typical photoionization experiment the wavelength of the applied EM
field is large compared to the size of the atom. This allows for a simplification,
which is called the dipole approximation:
2π
≫ a0
if λ = ⇒ eik·r ≈ 1
k
(3.36) e ∗
֒→ Bfdip
i = A hϕf |π̂ · p̂|ϕi i
2m 0
this can be rewritten by using
im
p̂ = [Ĥ0 , r] (3.39)
~
p2
for Ĥ0 = 2m
+ V (r)
im
֒→ hϕf |π̂ · p̂|ϕi i = hϕf |Ĥ0 π̂ · r̂ − π̂ · r̂Ĥ0 |ϕi i
~
im
= (ǫf − ǫi )π̂ · hϕf |r|ϕi i
~
The matrix elements in questions are the well-known dipole matrix elements
(cf. Sec. 2). For π̂ = ẑ we have the standard selection rules ∆m = 0, ∆l =
±12 . They result in characteristic angular dependencies of photoionized elec-
trons, e.g., (see assignment # 3)
dip,ẑ πe2
wi−→ f = |A0 |2 (ǫf − ǫi )2 ρ(ǫf )|hϕf |z|ϕi i|2
2~3
∝ cos2 θ
if the initital state is an s-state (l = 0).

Literature: [CT], Chap. XIII; [Lib], Chap. 13.5-13.9; [Sch], Chap. 11; [BS],
Chap. IV
Note that the notion of photons for the interpretation of photoionization
(and stimulated emission) has no significance as long as the analysis is based
on classical EM fields. From a theoretical point of view photons come into
the picture only if the EM field is quantized. This does not change the final
2
for other polarizations the m-selection rule changes, but the l-selection rule does not.
44
expressions for stimulated emission and absorbtion, but it shows that there
is another process which cannot be described in our semiclassical framework:
spontaneous emission, i.e., the emission of a photon (and transition to a
lower-lying state) without any external EM field. So, let’s take a look at
field quantization.
3.4 Outlook on field quantization

In the semiclassical framework we represented the EM field by classical po-
tentials (A, Φ), which act on the wave function of the electron(s). Now, we
want to derive a Hamiltonian that acts on the electron(s) and the EM field.
Accordingly, we need a wave function that includes the degrees of freedom
of the field.
Let’s start with the Hamiltonian. The generic ansatz for a system that
consists of two subsystems (atom and EM field in our case) which may in-
teract is as follows:
Ĥ = Ĥ1 + Ĥ2 + Ŵ
Ĥ = ĤA + ĤF +Ŵ (3.40)
| {z }
=Ĥ0
ĤA is the Hamiltonian of the atom, ĤF the (yet unknown) Hamiltonian of
the field, and Ŵ the interaction. We aim at a description of the problem
within first-order perturbation theory. So we know which steps we have to
take:
Steps for a first-order TDPT treatment
• determine Ĥ0
p̂2 √
(a) ĤA = 2m
+V
(b) ĤF =?
45
• solve eigenvalue problem of Ĥ0
√
ĤA |ϕj i = ǫj |ϕj i
ĤF |ξk i = εk |ξk i ? (3.41a)

֒→ Ĥ0 |Φjk i = ĤA + ĤF |ϕj i|ξk i
= (ǫj + εk ) |ϕj i|ξk i
= (ǫj + εk ) |Φjk i (3.41b)
While the first step (determining Ĥ0 ) is a physics problem, the second
one (solving Ĥ0 ’s eigenvalue problem) is a math problem.
• determine Ŵ
here it seems natural to start from the semiclassical expression (3.35)
and replace the classical vector potential by an operator that acts on
the degrees of freedom of the EM field
e
Ŵ = Â · p̂ (3.42)
m
Not surprisingly, it turns out that consistency with the form of ĤF
determines the form of Â
• apply FGR
the main issue here is to calculate the transition matrix elements
Wif = hΦf |Ŵ |Φi i (3.43)
a) Construction of ĤF
Loosely speaking, Hamiltonians are the quantum analogs of classical energy
expressions. Let’s look at the energy of a classical EM field in a cube of
volume L3
Z
1
WEM = (E · D + B · H)d3 r
2 L3
Z
ǫ0 1
= (E2 + c2 B2 )d3 r c2 = (3.44)
2 L3 µ0 ǫ0
46
Recall that free EM waves within Coulomb gauge (∇ · A = 0) are obtained

from
1 ∂2
∇2 A − A = 0
c2 ∂t2
Φ = 0
Instead of a monochromatic solution of the wave equation we consider the full
solution in L3 for periodic boundary conditions A(x, y, z = 0) = A(x, y, z =
L) etc. The latter are a convenient means to obtain a set of discrete modes
and discrete sums in all expressions instead of integrals:
X
A(r, t) = Aλ (r, t) (3.45a)
λ
π̂λ
ℜ3 ∋ Aλ (r, t) = 3 qλ ei(kλ r−ωλ t) + qλ∗ e−i(kλ r−ωλ t) (3.45b)
L2
λ mode index
π̂λ unit polarization vectors |π̂λ | = 1
2π
kλ = L
(nλx , nλy , nλz ) nλi ∈ Z wave vectors and numbers
ωλ = ckλ field frequencies
π̂λ · kλ = 0 → transverse waves

Each mode is thus defined by a wave vector (with three components) and a
polarization direction3 . If one uses this explicit form of A to calculate
E(r, t) = −∂t A(r, t)
B(r, t) = ∇ × A(r, t)
and plugs this into Eq. (3.44) one arrives at
X
WEM = 2ǫ0 ωλ2 qλ∗ qλ (3.46)
λ
3
this is to say that λ is actually a quadruple index. Note that for the general solution
of the wave equation we need two linearly independent polarizations per wave vector.
This can be made more explicit by a somewhat more elaborate notation, see, e.g. [Sch],
Chap. 14.
47
Obviously, the EM energy doesn’t change with time—this is another (conve-

nient) consequence of using periodic boundary conditions.
The next step is a transformation to real amplitudes:
√
Qλ := ǫ0 (qλ∗ + qλ ) (3.47)
√
Pλ := i ǫ0 ωλ (qλ∗ − qλ ) (3.48)

1 Pλ
⇔ qλ = √ Qλ + i (3.49)
2 ǫ0 ωλ

1 Pλ
qλ∗ = √ Qλ − i (3.50)
2 ǫ0 ωλ

1 X 2 Pλ Pλ
֒→ WEM = ωλ (Qλ + i ) Qλ − i (3.51)
2 λ ωλ ωλ
1 X
= Pλ2 + ωλ2 Q2λ (3.52)
2 λ
Doesn’t this look familiar? The EM field has the algebraic form of a collection
of harmonic oscillators. We know how to quantize the harmonic oscillator,
so here is the quantization recipe:
Pλ → P̂λ = P̂λ† (3.53)

Qλ → Q̂λ = Q̂†λ (3.54)
with [Q̂λ , P̂λ′ ] = i~δλλ′ (3.55)
1 X 2
֒→ WEM → ĤF = P̂λ + ω 2 Q̂2λ = ĤF† (3.56)
2 λ
The algebraic form of ĤF together with the commutation relations (3.55)
determine its spectrum:

X 1
En1 ,n2 ,... = ~ ωλ nλ + nλ = 0, 1, 2, ...
λ
2
The standard QM interpretation would be to associate each mode with a

particle trapped in a parabolic potential. The energies Enλ = ~ ωλ (nλ + 21 )
48
would then correspond to the ground- and the excited-state levels of that
particle. However, it is not clear what kind of particle this should be, since
Qλ and Pλ do not correspond to usual position and momentum variables
(and actually there is no parabolic potential around).
The fact that the spectrum is equidistant allows for an alternate inter-
pretation, in which each mode is associated with nλ ’quanta’ 4 , each of which
carries the energy ~ωλ . In this interpretation a mode does not have a ground
state and excited states, but is more like a (structureless) container that can
accomodate (any number of) quanta of a given energy. The quanta are called
photons. At this point their only property is that they carry energy, but
we will see later that there is more in store. Note that the photon inter-
pretation is only possible because the spectrum of the harmonic oscillator is
equidistant!
nλ : occupation
P number of mode λ
N = λ nλ : total number of photons in the field
However, even without any photon around there is energy, unfortunately

even an infinite amount:
X ~ ωλ
zero-point energy E0 = → ∞ (3.57)
λ
2
A proper treatment of this infinite zero-point energy requires a so-called
renormalization procedure. We will not dwell on this issue, but (try to) put
our minds at ease with the remark that normally only energy differences have
physical significance5 . These are always finite since the zero-point energies
cancel.
b) Creation and annihilation operators
For the further development it is useful to introduce creation and annihilation
operators:
1
b̂λ = √ (ωλ Q̂λ + iP̂λ ) anniliation op. (3.58)
2~ ωλ
1
b̂†λ = √ (ωλ Q̂λ − iP̂λ ) creation op. (3.59)
2~ ωλ
4
you may say particles instead of quanta, but these particles turn out to have an odd
property: zero rest mass.
5
In fact, renormalization is not much more than a more formal way of adopting this
viewpoint.
49
Let’s play with them and look at their commutators, e.g.

h i 1 h i
†
∢ b̂λ , b̂λ = ωλ Q̂λ + iP̂λ , ωλ Q̂λ − iP̂λ
2~ ωλ  

 
1  h i h i

= −iωλ Q̂λ , P̂λ +iωλ P̂λ , Q̂λ
2~ ωλ 
 | {z } | {z } 
 
i~ −i~
1
= {~ ωλ + ~ ωλ } = 1
2~ ωλ
h i
†
⇒ b̂λ , b̂λ′ = δλλ′ (3.60)
h i
b̂λ , b̂λ′ = 0 (3.61)
h i
† †
b̂λ , b̂λ′ = 0 (3.62)
֒→ rewrite the Hamiltonian

1X 2
ĤF = P̂λ + ω 2 Q̂2λ
2 λ

1X ~ ωλ † 2 ~ ωλ † 2
= − (b̂λ − b̂λ ) + (b̂λ + b̂λ )
2 λ 2 2
1X
= ~ ωλ b̂†λ b̂λ + b̂λ b̂†λ (3.63)
2
λ
X 1
= ~ ωλ (b̂†λ b̂λ + )
λ
2
X 1
= ~ ωλ (n̂λ + ) (3.64)
λ
2
n̂λ = b̂†λ b̂λ is called occupation number operator.

h i
Obviously ĤF , n̂λ = 0 ∀ λ, i.e., they have the same eigenstates. Let’s
50
first consider a single mode only:

X
ĤF = ĤFλ
λ
1
ĤFλ |ψnλ i = ~ ωλ (nλ + ) |ψnλ i (3.65)
2
with nλ ∈ N0
Usually, one uses a short-hand notation for the eigenstates and writes
|ψnλ i ≡ |nλ i. These states are called (photon) number or Fock states. Note
that |ψ0 i ≡ |0i is not a vector of zero length, but the (ground) state as-
sociated with the statement that there are no photons in the mode (but
energy E0 = ~ωλ /2). As eigenstates of a hermitian operator the |nλ i fulfill
an orthonormality relation
hnλ |n′λ i = δnλ n′λ (3.66)
!
ĤFλ − 12
֒→ nˆλ |nλ i = nλ |nλ i n̂λ = (3.67)
~ ωλ
nˆλ |0i = 0|0i = 0 this is a real zero! (3.68)
The eigenvalue nλ is the number of photons in the mode. This justifies the
name occupation number operator for n̂λ .
Let’s operate with creation and annihilation operators on these photon
number states. To do this we need a few relations that can be proven without
difficulty.
h i
b̂λ , n̂λ′ = b̂λ δλλ′ (3.69)
h i
b̂†λ , n̂λ′ = −b̂†λ δλλ′ (3.70)

∢ n̂λ b̂λ |nλ i = b̂†λ n̂λ |nλ i + b̂†λ |nλ i
†

= (nλ + 1) b̂†λ |nλ i
51
obviously, the vector b̂†λ |nλ i is an eigenstate of nλ with the eigenvalue

(nλ + 1). On the other hand:
n̂λ |nλ + 1i = (nλ + 1) |nλ + 1i
֒→ combine:
b̂†λ |nλ i = α |nλ + 1i

⇒ |α|2 hnλ + 1|nλ + 1i = hnλ | b̂λ b̂†λ |nλ i
| {z }
=1
= hnλ | n̂λ + 1 |nλ i
= nλ + 1
√
⇔ α= nλ + 1
√
֒→ b̂†λ |nλ i = nλ + 1 |nλ + 1i (3.71)
This justifies the notion creation operator: operating with it on a number

state creates one additional photon. Similarly one finds
√
b̂λ |nλ i = nλ |nλ − 1i (3.72)
to be consistent with Eq. (3.68) we stipulate
b̂λ |0i = 0
Generalization:
ĤF |n1 , n2 , ...i = E |n1 , n2 , ...i (3.73)

X
X 1
E = ~ ωλ nλ + = ~ ωλ nλ + E0 (3.74)
2
λ λ
|n1 , n2 , ...i = |n1 i |n2 i... product states (3.75)
nˆλ |... nλ ...i = nλ |... nλ ...i (3.76)

√
b̂†λ |... nλ ...i = nλ + 1 |... nλ + 1 ...i (3.77)
√
b̂λ |... nλ ...i = nλ |... nλ − 1 ...i (3.78)
52
c) Interaction between electron(s) and photons

We start from Eq. (3.42) and require that the quantization of the vector
potential be consistent with the quantization of the EM energy. The latter
implies the following quantization rule for the amplitudes:
! r
1 P̂λ ~
qλ → q̂λ = √ Q̂λ + i = b̂λ (3.79)
2 ǫ0 ωλ 2ǫ0 ωλ
which yields
r
X ~ i(kλ ·r−ωλ t) † −i(kλ ·r−ωλ t)
Â(r, t) = π̂λ b̂λ e + b̂λ e (3.80)
λ
2ωλ ǫ0 L3
The time dependence of Â is the time dependence of an operator in the

Heisenberg picture. The corresponding Schrödinger operator reads
r
X ~ ikλ ·r † −ikλ ·r
Â(r) = π̂λ 3
b̂λ e + b̂λ e (3.81)
λ
2ω λ ǫ0 L
The latter is used in the interaction potential:

e
Ŵ = Â · p̂
m s
X e2 ~3 n
ikλ ·r † −ikλ ·r
o
= −i π̂λ b̂λ e ∇ + b̂λ e ∇ (3.82)
λ
2ωλǫ0 m2 L3
Not surprisingly, the interaction has a part that acts on the electron and a
part that acts on the photons. The electronic part is the same as in the semi-
classical treatment. The photonic part involves the creation or annihilation
of a photon in the mode λ.
d) Transitions matrix elements
We need
X
Wif = hΦf |Ŵ |Φi i = hΦf |Ŵλ |Φi i
λ
s
e2 ~3
hΦf |Ŵλ |Φi i = −i
2ωλ ǫ0 m2 L3
× {hϕf | eikλ ·r π̂λ · ∇ |ϕi i hnf1 ... nfλ ...| b̂λ |ni1 ... niλ ...i
+hϕf | e−ikλ ·r π̂λ · ∇ |ϕi i hnf1 ... nfλ ...| b̂†λ |ni1 ... niλ ...i}
53
The electronic matrix elements are the same as in the semiclassical frame-
work. We have discussed them in dipole approximation in Sec. 3.3. Let’s look
at the photonic matrix elements. Basically, they result in selection rules:
q
hn1 ... nλ ...| b̂λ |n1 ... nλ ...i = niλ hnf1 ... nfλ ...|ni1 ... niλ − 1 ...i (3.83)
f f i i
noting that hnf |ni i = δf i in each mode one obtains

q
f f i i
hn1 ... nλ ...| b̂λ |n1 ... nλ ...i = niλ δnf ni δnf ni ...δnf ni −1 ... (3.84)
1 1 2 2 λ λ
and similarly
q
hnf1 ... nfλ ...| b̂†λ |ni1 ... niλ ...i = niλ + 1 δnf ni δnf ni ...δnf ni +1 ... (3.85)
1 1 2 2 λ λ
We obtain a nonvanishing contribution only if the number of photons in

one mode λ differs by one in the initial and final states, but is the same in
all other modes. Obviously, the annihilation process (3.84) corresponds to
photon absorption (one photon less in the final state than in the initial state)
and the creation process (3.85) to photon emission (one photon more in the
final state than in the initial state).
Summary:
hΦf |Ŵ |Φi i =
6 0 iff
1. the photon numbers in |Φi i and |Φf i differ exactly by one in one single
mode. Otherwise orthogonality will kill the transition amplitude. This
is to say that first-order perturbation theory accounts for one-photon
processes only.
2. dipole selection rules are fulfilled for the crucial mode (assuming that
eikλ ·r ≈ 1).
3. energy conservation is fulfilled: Ei = Ef . This follows from the fact

that the total Hamiltonian is time independent and is also consistent
with the application of TDPT for a time-independent perturbation (cf.
example (ii) of Sec. 3.2 b)).
54
Elaborate on energy conservation: noting that the energy eigenvalues of elec-

tronic and photonic parts add (cf. Eq. (3.41b)) we find

X
i 1
Ei = ǫi + ~ωλ′ nλ′ + (3.86)
2
λ′

X f 1
Ef = ǫf + ~ωλ′ nλ′ + (3.87)
λ ′
2
Ei = Ef ⇔ ǫf = ǫi ± ~ωλ (3.88)
with the plus sign for absorption and the minus sign for emission.
e) Spontaneous emission
∢ |Φi i = |ϕi i|0, 0, . . .i
Even if there is no photon around in the initial state we can obtain a
nonvanishing transition matrix element by operating with a creation operator
on the vacuum state |0, 0, . . .i. This corresponds to the process of spontaneous
emission: an excited electronic state decays by (one-) photon emission even
though no external radiation field is present. One may say that it is the
zero-point energy in the given mode that triggers the transition.
For the investigation of the quantitative aspects of spontaneous emission
one uses FGR (3.38). The transition rate can be written as
s.e. 2π
wi−→f = |Wf i |2 ρ(ef ) (3.89)
~s
e2 ~3
Wf i = −i hϕf |e−ikλ ·r π̂λ · ∇|ϕi i (3.90)
2ωǫ0 m2 L3
ǫf − ǫi
with ω =
~
The density of states in FGR refers to the photon density in the final states.
To calculate it recall
2π λ λ λ
kλ = (n , n , n ) nλi ∈ Z
L x y z
3
∆N ∆nx ∆ny ∆nz L
֒→ ρ(k) = = =
∆V ∆kx ∆ky ∆kz 2π
55
We need ρ = ρ(ef ), i.e., we need to transform to energy space:

dk
dV = d3 k = k 2 dkdΩk = k 2 def dΩk
def
dk 1
photons: ef = ~ω = ~ck → =
def ~c
3 2 3 2
3 L k L ω
֒→ dN = ρ(k)d k = def dΩk = def dΩk ≡ ρ(ef )def dΩk
2π ~c 2π ~c3
Inserting this into Eq. (3.89) one obtains for the (differential) spontaneous
emission rate (for a given polarization π̂):
s.e.,π̂
dwi−→f e2 ~ω
= 2 |hϕf |e−ikλ ·r π̂λ · ∇|ϕi i|2
dΩk 8π ǫ0 m2 c3
In dipole approximation (using once again Eq. (3.39)) this reduces to
s.e.,π̂
dwi−→f e2 ω 3
= |π̂ · rif |2 (3.91)
dΩk 8π 2 ǫ0 ~c3
rif = hϕf |r|ϕi i (3.92)
The total rate is obtained by integrating (3.91) over dΩk and summing over
two perpendicular (transverse) polarizations. The final result for the inverse
s.e.
lifetime 1/τi→f = wi−→f is
dip
1 e2 ω 3
= | rif |2 . (3.93)
τ i→f 3πǫ0 ~c3
Examples:
• Lifetime of H(2p)
dip
τ2p→1s ≈ 1.6 · 10−9 s
This looks like a short lifetime, but compare it to the classical revolution
time of an electron in the hydrogen ground state!
st
1 order
• τ2s→1s → ∞
For the transition rate 2s → 1s one finds a strict zero for the first-order
rate even beyond the dipole approximation. Experimentally one finds
τ2s→1s ≈ 0.12s. Theoretically, one obtains this number in a second-
order calculation, in which two-photon processes are taken into account.
56
This expresses to a general pattern: an N-photon process corresponds to

an N-th order TDPT amplitude.
f) Concluding remarks on photons
What have we learned about photons (associated with a given mode)?
• they can be created and annihilated (i.e. they don’t last forever)
• they carry energy ~ωλ
• they carry momentum ~kλ

this can be shown by starting from the classical expression for the total
momentum of the free electromagnetic field
Z
PEM = ǫ0 E × B d3 r
L3
using similar arguments as for the translation of WEM to Ĥf one obtains
X
P̂F = ~kλ n̂λ
λ
and X
P̂F |n1 , n2 , . . .i = ~kλ nλ |n1 , n2 , . . .i
λ
• they carry angular momentum (called spin) ±~

this can be shown by starting from the classical expression for the total
angular momentum of the free electromagnetic field
Z
LEM = ǫ0 r × E × B d3 r
L3
using similar arguments as for the translation of WEM to Ĥf . However,

this calculation requires a more explicit consideration of different pos-
sible polarization directions (which are not obvious in our condensed
λ-notation).
• photons are bosons!

The spin-statistics theorem shows that particles with integer spin ful-
fill Bose-Einstein statistics. There is no restriction on the number of
57
bosons (photons) which can occupy a given state (mode)—we have’nt

encountered an upper limit for the occupation numbers nλ . One can
set up a similar (occupation number) formalism for many-electron sys-
tems and finds that in this case the occupation numbers can only be 0
or 1 due to the Pauli principle for fermions.
• Finally, we add that photons travel with v = c (because free EM waves

do) and thus must have zero mass (to avoid conflicts with Einstein’s
theory of relativity).
• literature on field quantization:

relatively simple accounts on the quantization of the EM field can be
found in [Fri], Chap. 2.4 and [SN], Chap. 7.6
’higher formulations’: [Sch], Chap. 14; [Mes], Chap. 21 (and, of course,
QED textbooks)
Chapter 4
Brief introduction to
relativistic QM
Literature: [BD]; [BS], Chap. 1.b; [Mes], Chap. 20; [Sch], Chap. 13; [Lib],
Chap. 15; [SN], Chap. 8
The first reference is a classic textbook. The latter book chapters provide
condensed accounts on relativistic quantum mechanics.
4.1 Klein-Gordon equation

a) Setting up a relativistic wave equation
• starting point: classical relativistic energy-momentum relation1
E 2 = p2 c2 + m2 c4 (4.1)
• quantization : E −→ i~∂t
~
(standard rules) p −→ ∇
i
֒→ p2 −→ −~2 ∇2
֒→ E 2 −→ −~2 ∂t
1
In the following, m always denotes the rest mass m0 .
58
59
• obtain (free) wave equation (Klein-Gordon equation (KGE))
−~2 ∂t2 ψ(r, t) = −~2 c2 ∆ψ(r, t) + m2 c4 ψ(r, t) (4.2)
The KGE was first obtained by Schrödinger in the winter of 1925/26,

but abandoned due to problems. Schrödinger then concentrated on
the nonrelativistic case and found his equation, while the KGE was
rediscovered a bit later by Klein and (independently) by Gordon.
b) Discussion
1. KGE is second-order PDE wrt. space and time

2. KGE is Lorentz covariant
∂ψ
3. Time development is determined from initial conditions ψ(t0 ), (t ),
∂t 0
which is at odds with evolution postulate of QM
4. Continuity equation?
−→ one can derive ∂t ρ + divj = 0
i~
with standard current j = 2m
(ψ∇ψ ∗ − ψ ∗ ∇ψ)
i~
but : ρ= (ψ ∗ ∂t ψ − ψ∂t ψ ∗ ) (4.3)
2mc2
problem: ρ(rt) ≷ 0 (i.e. not positive definite)
−→ probabilistic interpretation is not possible (or at least not obvious)
5. Ansatz (i)
ψ(r, t) = Aei(kr−ωt)
−→ insertion into Eq. (4.2) yields together with de Broglie relations
√
E = ~ω = ± c2 ~2 k2 + m2 c4 ≶ 0 (4.4)
ρ and j are okay (check!), but what does E < 0 signify?

Ansatz (ii)
ψ(r, t) = Ae−i(kr−ωt)
results in the same expression for E, but corresponds to ρ < 0 (check!).
Ansatz (iii)
ψ(r, t) = A sin(kr − ωt)
60
also results in the same expression for E, but corresponds to ρ = 0,

j = 0 (check!).
6. Add Coulomb potential to free KGE and solve it (in spherical coordi-
nates)
−→ yields wrong fine structure of hydrogen spectrum (i.e., contradicts
experimental findings)
7. In 1934, the KGE was recognized as the correct wave equation for
spin-zero particles (mesons).
4.2 Dirac equation

In 1928, Dirac found a new wave equation which is suitable for electrons
(spin 21 -particles): the Dirac equation (DE)
a) Free particles
ansatz : i~∂t Ψ = ĤD Ψ (4.5)

st
i.e. stick to the form of the TDSE; a PDE of 1 order in t such that Ψ(t0 )
is the only initial condition
requirements (Dirac’s wish list):

1. DE must be compatible with energy-momentum relation (4.1)
2. DE must be Lorentz-covariant
3. Obtain continuity equation with probabilistic interpretation
4. Stick to the usual quantization rules!
Dirac recognized that these requirements cannot be satisfied by a single scalar
equation, but by a matrix equation for a spinor wave function with N com-
ponents.
ansatz : ĤD = cα · p̂ + βmc2 (4.6)
3
c~ X
= αi ∂xi + βmc2
i j=1
61
with N × N matrices αx , αy , αz , β and spinor wave function

 
ψ1 (r, t)
Ψ=
 .. 
as solution of (4.5)
. 
ψN (r, t)
֒→ requirement (1) is met if each component ψi solves KGE (4.2)

−→ iterate Eq. (4.5):
i~∂t (i~∂t Ψ) = ĤD (ĤD Ψ)
c~ X c~ X
֒→ −~2 ∂t2 Ψ = αj ∂xj + βmc2 αk ∂xk + βmc2 Ψ
i j
i k
n X ~ 3X o
2 2 2 2 4
= −~ c αj αk ∂xj ∂xk + mc αj β + βαj ∂xj + β m c Ψ
i j
jk
X αj αk + αk αj ~mc3 X
= −~2 c2 ∂x2j xk Ψ + β 2 m2 c4 Ψ + (αj β + βαj )∂xj Ψ
2 i j
jk
comparison with KGE yields conditions for αi , β:
αj αk + αk αj = 2δjk (4.7)
αj β + βαj = 0 (4.8)
αj2 = β 2 = 1 (4.9)
further conditions and consequences:
• αj , β hermitian (because ĤD shall be hermitian)

=⇒ real eigenvalues
4.9
=⇒ eigenvalues are ±1
• from (4.7)-(4.9) it follows that αj , β are ’traceless’, i.e.

tr αj = tr β = 02
• together with eigenvalues ±1 this implies that dimension N is even

2
The trace of a matrix A is defined as the sum over P
the diagonal elements. The trace
does not change when A is diagonalized. Hence tr A = eigenvalues.
62
• N = 2 is too small as there are only three ’anti-commuting’ (Eqs. (4.7)

and (4.8)) matrices for N = 2 (the Pauli matrices). Dirac needs four!
• try N = 4
• derive explicit representations from these conditions
 
1 0
0 σi  1 
֒→ αi = , β=  (4.10)
σi 0  −1 
0 −1
with Pauli matrices σi

0 1 0 −i 1 0
σx = , σy = , σz =
1 0 i 0 0 −1
=⇒ free DE takes the form

   
ψ1 ψ1
 ψ2
 = (cα · p̂ + βmc2 )  ψ2 
  
i~∂t 
 ψ3   ψ3  (4.11)
ψ4 ψ4
and one can derive a meaningful continuity equation:
∂t ρ + divj = 0
4
X
with ρ = Ψ† Ψ = ψ ∗ (r, t)ψ(r, t)
i=1
†
and j = cΨ αΨ

ψ1
0 σk  ψ2  )

( i.e. jk = c(ψ1∗ , ψ2∗ , ψ3∗ , ψ4∗ )
σk 0  ψ3 
ψ4
b) Solutions of the free DE
Ansatz : ψj (r, t) = uj ei(kr−ωt) , j = 1, ..., 4

after some calculation one finds:
63
• there are 4 linear independent solutions.

p
Two correspond to E = + p2 c2 + m2 c4
p
and two to E = − p2 c2 + m2 c4
• they have the form (E > 0):

  
1 0
 0   1 
u(1) = 
 χ1
 ,
 u(2) = 
 χ′1 
χ2 χ′2
and for E < 0:

 
ϕ1 ϕ′1
 ϕ2   ϕ′2 
u(3)  1  ,
=  u(4) =
 0 

0 1
with
cpz c(px + ipy ) c(px − ipy )
χ1 = 2
, χ2 = 2
, χ′1 = , χ′2 = −χ1
E + mc E + mc E + mc2
cpz c(px + ipy ) c(px − ipy )
ϕ1 = 2
, ϕ2 = 2
, ϕ′1 = 2
, ϕ′2 = −ϕ1
E − mc E − mc E − mc
note that all these ’small components’ approach zero for v ≪ c.
u(1) , u(3) are interpreted as ’spin up’
u(2) , u(4) are interpreted as ’spin down’ solutions
E e e
2
m 0 c
5 1 1 k e V fo r e
0
2
h o le
-m 0 c
D ira c s e a
Figure 4.1: Energy spectrum of the free DE

64
Dirac’s interpretation(1930):
In the vacuum all negative energy states (in the Dirac sea) are occupied.
Hence, if electrons are present at E > mc2 they cannot ”fall down” into the
Dirac sea because of the Pauli principle (electrons are fermions).
On the other hand, one can imagine that it is possible to excite one
electron from the Dirac sea to E > mc2 . Such an excitation corresponds
to a hole in the Dirac sea, which can be interpreted as the presence of a
positively charged particle — an anti-particle (i.e. a positron). This process
— electron-positron pair creation — has indeed been observed, and also the
reversed process — destruction of electron-positron pairs and γ-ray emission
(the latter to balance the total energy).
In fact, the first experimental detection of positrons in 1932 was consid-
ered a strong proof of Dirac’s theory.
c) Throw in (classical) EM potentials
use the ’minimal coupling prescription’
~
p −→ ∇ + eA = p̂ + eA
i
E −→ i~∂t + eφ
(4.11)
n o
2
֒→ i~∂t Ψ = cα̂ · (p̂ + eA) − eφ + βmc Ψ (4.12)
one can show that Eq. (4.12) is Lorentz-covariant.

d) The relativistic hydrogen problem
Consider Eq. (4.12) with A = 0 and
Ze
φ=
4πǫ0 r
i
ansatz : Ψ(r, t) = Φ(r)e− ~ Et
(4.13)
yields
n Ze2 o
−→ cα̂ · p̂ + βmc2 − Φ(r) = EΦ(r) (4.14)
4πǫ0 r
this stationary DE can be solved analytically!
65
Result for the bound spectrum (−→ fine structure):

" #− 21
2
(Zα)
Enj = mc2 1 + n = 1, 2, ... (4.15)
(n − δj )2
r
1 1 2 1 3 1
δj = j + − j+ − (Zα)2 , j = , , ...n − (4.16)
2 2 2 2 2
n (still) is the principal quantum number, while j can be identified as quan-
tum number of total angular momentum.
~ e2 1
α= = ≈ (4.17)
mca0 4πǫ0 ~c 137
fine-structure constant
expansion of Eq. (4.15) in powers of (Zα)2 ≪ 1:
" #
2 4
(Zα) (Zα) 1 3
Enj = mc2 1 − − − ± ... (4.18)
2n2 2n3 j + 21 4n
1st term: rest energy
2nd term: non-relativistic binding energy (1.23)
3rd term: lowest order relativistic corrections −→ fine structure splitting
of energy levels
2
E = m 0 c
3 s3 p 3 d
n = 3
3 d 5 /2
2 s2 p 3 p 3 /2 3 d 3 /2
n = 2 3 s 1 /2 3 p 1 /2
2 p 3 /2
2 s 1 /2 2 p 1 /2
1 s 1 .8 x 1 0 -4
e V
n = 1
1 s 1 /2
S c h rö d in g e r D ira c
Figure 4.2: Energy spectrum of the Coulomb problem

66
Further corrections (beyond DE)3 :

• hyperfine structure (coupling of magnetic moments of electron(s) and
nucleus)
∼ 10−6 eV
• QED effects (Lamb shift): further splitting of levels with same j, but
different l quantum numbers
∼ 10−6 eV
e) Nonrelativistic limit of the DE

Instead of solving Eq. (4.14) exactly and subsequently expanding the ex-
act eigenvalues (4.15) it is useful to consider the non- (or rather: weak-)
relativistic limit of the stationary DE (4.14) and to account for the lowest-
order relativistic corrections obtained in this way in 1st -order perturbation
theory. This procedure yields the same result (4.18) once again, but this
time it comes with an interpretation regarding the nature of the relativistic
corrections.
Starting point: stationary DE

n o
2
cα̂ · p̂ + βmc + V (r) Φ(r) = EΦ(r) (4.19)
group the 4-component spinor according to

ϕ ϕ1 χ1
Φ= , with ϕ = , χ=
χ ϕ2 χ2
insert into (4.19) (using similar groupings of the Dirac matrices in terms of
Pauli matrices):
n o
0 σ ϕ 2 1 0 ϕ
֒→ c · p̂ = E − V (r) − mc (4.20)
σ 0 χ 0 1 χ
⇐⇒
cσ · p̂ χ = (E − V (r) − mc2 )ϕ (4.21)

cσ · p̂ ϕ = (E − V (r) + mc2 )χ (4.22)
3
for details see [BS]
67
Solve (4.22) for χ and insert into (4.21):
c2
֒→ σ · p̂ σ · p̂ ϕ = (E − V (r) − mc2 )ϕ (4.23)
E − V (r) + mc2
• define ε = E − mc2 ≪ mc2
• assume V (r) ≪ mc2
• expand

c2 c2 1 1 ε − V (r)
2
= 2
= ε−V (r)
≈ 1−
E − V (r) + mc ε + 2mc − V (r) 2m(1 + 2mc2 ) 2m 2mc2
use all this in (4.23) to obtain

1 ε − V (r)
σ · p̂ 1 − σ · p̂ ϕ = (ε − V (r))ϕ
2m 2mc2
• apply the product rule for p̂[V (r)ϕ]
• use the following identity for Pauli matrices and arbitrary vector oper-
ators Â, B̂
(σ · Â)(σ · B̂) = Â · B̂ + iσ · (Â × B̂)
• use for a central potential

1 dV
∇V (r) = r
r dr
to obtain
(T1 + T2 + T3 )ϕ = (ε − V (r))ϕ
with

ε − V (r) p̂2
T1 = 1− (4.24)
2mc2 2m
~ 1 dV
T2 = (σ · l̂) (4.25)
4m2 c2 r dr
~ 1 1 dV
T3 = (r · p̂) (4.26)
i 4m2 c2 r dr
68
Interpretation of terms
• For the interpretation of T1 note that
p̂2
(ε − V (r))ϕ ≈ ϕ
2m
p̂2 p̂4
֒→ T1 = − ≡ T̂N R + ĤKE (4.27)
2m 8m3 c2
ĤKE represents the lowest-order relativistic correction to the kinetic
energy (as it appears — without hats — in a classical treatment).
• Introducing the spin operator ŝ = ~2 σ, which due to the properties
of the Pauli matrices fulfills the standard commutation relations of an
angular momentum operator4 , T2 is identified as the spin-orbit coupling
term
T2 ≡ ĤSO .
Hence, spin and spin-orbit coupling are automatically included in a
relativistic treatment (which is why some authors insist that electron
spin is a relativistic property).
• T3 is not hermitian. Consider its hermitian average

T3 + T3† 1 ~ 1 dV ~ 1 dV
T̄3 = = (r · p̂) − (p̂ · r)
2 8m2 c2 i r dr i r dr
2
~
= ∇2 V (r) ≡ ĤDarwin .
8m2 c2
The Darwin term doesn’t have a nonrelativistic or classical counterpart.
It is usually associated with the ”Zitterbewegung” (trembling motion)
of the electron due to the nonzero coupling of electrons and positions
(or: large and small components of the Dirac spinor) [BD].
Now apply perturbation theory to the problem
Ĥ = Ĥ0 + Ŵ (4.28)
2 2
p̂ Ze
Ĥ0 = T̂N R + V (r) = − (4.29)
2m 4πǫ0 r
Ŵ = ĤKE + ĤSO + ĤDarwin (4.30)
4
for a recap of angular momentum and spin operators consult a QM textbook, e.g.
[Gri], Chaps. 4.3, 4.4
69
One obtains for the first-order energy correction
mc2 1 3
∆E (1) = − (Zα) 4
1 − , (4.31)
2n3 j+ 2
4n
i.e., the same results as in Eq. (4.18), which shows the consistency of the
approach.
Chapter 5
Molecules
A simple man’s definition of a molecule says that it is an aggregate of atoms

which cling together by bonds. The big question then is: why are the atoms
doing this, i.e., what is the nature of the chemical bond? It turns out that
this can only be answered satisfactorily by quantum mechanics.
We should thus start by insisting that molecules are quantum-mechanical
many-body systems consisting of M ≥ 2 atomic nulcei and N ≥ 1 electrons,
which interact with each other (mainly) by Coulomb forces. Let’s assume
that the Coulomb force is the only force present and that everything can be
described nonrelativistically.
Hamiltonian:
Ĥ = T̂nuc + T̂el + V (5.1)

M M
X P̂2α ~2 X 1 2
T̂nuc = =− ∇ (5.2)
α=1
2Mα 2 α=1 Mα Rα
M N
X p̂2 ~2 X 2
T̂el = =− ∇ (5.3)
i=1
2me 2me i=1 ri
V = Vnn + Vne + Vee (5.4)
M
X Zα Zβ e2
Vnn = (5.5)
4πǫ0 |Rα − Rβ |
α<β
M X
N
X Zα e2
Vne = − (5.6)
α=1 i=1
4πǫ0 |Rα − ri |
70
71
N
X e2
Vee = (5.7)
i<j
4πǫ0 |ri − rj |
The task is to solve the stationary Schrödinger equation

Ĥ |Φi = E |Φi (5.8)
for this Hamiltonian. This would be a complicated problem, but one doesn’t
really have to do it in most situations of interest.
5.1 The adiabatic (Born-Oppenheimer) ap-

proximation
The adiabatic (or: Born-Oppenheimer) approximation forms the basis for
the discussion of molecular structure and properties. It exploits the large
mass difference between electrons and nuclei.
a) Prelude
Let’s consider the (drastic) approximation of infinitely heavy nuclei which
cannot move:
Mα → ∞ ⇒ T̂nuc → 0 .
We are left with the simpler ”electronic” SE

T̂el + V (R) Ψn (r, R) = En (R)Ψn (r, R) (5.9)
with r = (r1 , r2 , ..., rN ) and R = (R1 , R2, ..., RM ).

Remarks
1. The nuclear coordinates R are now ’external’ parameters (no inde-
pendent variables). The electronic wave functions Ψn and the energy
eigenvalues depend parametrically on R.
2. Actually, we should use a better notation that accounts for the elec-
trons’ spins, e.g., r → x = (r1 s1 , ...rN sN ), since the spin coordinates
play a role for the permutation symmetry of many-electron systems
(even though spin-dependent interactions are neglected). We don’t do
it for the sake of simplicity, since the arguments used in this section
are independent of symmetry and spin.
72
3. Since T̂el +V (R) is hermitian, the Ψn form a complete (and orthogonal)

basis for any configuration {R} of the nuclei. We can write, e.g.,
hΨm | Ψn ir = h Ψm (R)| Ψn (R)ir

Z
= Ψ∗m (r1 , r,2 , ...rN , R)Ψn (r1 , r,2 , ...rN , R)d3r1 d3 r2 ...d3 rN
= δmn
b) Adiabatic approximation: separation of electronic and nuclear motion

Back to the full problem.
X
Ansatz: Φ(r, R) = φn (R)Ψn (r, R) (5.10)
n
Sub into Eq. (5.8), multiply everything by Ψ∗n (r, R), use Eq. (5.9) and inte-
grate over electronic coordinates choosing Ψ∗n (r, R) = Ψn (r, R) such that
∇Rα hΨm | Ψm ir = h ∇Rα Ψm | Ψm ir + hΨm |∇Rα | Ψm ir

⇔ 0 = 2 hΨm |∇Rα | Ψm ir
to obtain
X
T̂nuc + Em (R) + ∆m (R) − E) φm (R) = Ĉmn (R)φn (R) (5.11)
n6=m
with definitions
D E

∆m (R) = Ψm (R) T̂nuc Ψm (R)
r
X ~2
Ĉmn (R) = α
(Aαmn (R) · ∇Rα + Bmn (R))
α
Mα
Aαmn (R) = hΨm |∇Rα | Ψn ir

α 1

Bmn (R) = Ψm ∇2Rα Ψn r
2
The adiabatic approximation consists in neglecting all the coupling terms:
X
Ĉmn (R)φn (R) ≈ 0 . (5.12)
m6=n
73
Hence, we arrive at two SEs; one for the electronic and one for the nuclear
motion:

T̂el + V (R) Ψm (r, R) = Em (R)Ψm (r, R) (5.13)

T̂nuc + Um (R) φm (R) = Eφm (R) (5.14)
Um (R) = Em (R) + ∆m (R) . (5.15)
The third equation provides the connection of the two SEs. This set of
equations is the standard framework for the discussion of molecular structure
and properties.
Discussion
• ,,Born-Oppenheimer approximation” (BOA): adiabatic approximation

plus assumption ∆m (R) ≈ 0.
→ ”potential energy surfaces” (PES) Em (R) determine nuclear motion:
"antibonding"
R
De E 0 (R)
"bonding"
• Re
Figure 5.1: Typical PESs for M = 2 (Em (R) = Em (R)) as functions of the
internuclear distance R.
For R → ∞ all PESs become horizontal (vanishing Coulomb forces),

for R → 0 all PESs increase like R1 because Vnn dominates. The mini-
mum of the lower (ground-state) curve corresponds to the equilibrium
distance (bond length) of the molecule.
me
• Gist and justification of BOA: M α
≈ 10−4
The nuclei are so slow that they feel only an average electronic field
74
(via the PESs). The fast electrons follow the slow nuclear motion adi-
abatically, i.e., without undergoing transitions.
A closer inspection of the BOA shows that the neglected terms ∆m (R)
and Ĉmn (R) are proportional to the smallness parameter 1/Mα .
5.2 Nuclear wave equation: rotations and vi-

brations
Let’s consider a diatomic molecule (M = 2). The structure of the problem
is that of a two-body central-field problem. Hence, we can reduce it to an
effective one-body problem using CM and relative coordinates (cf. Chaps. 1.1
and 1.2). The nontrivial SE for the relative (internal) motion reads
2
!
P̂ R
Eφn (R) = + Un (R) φn (R)
2µ
2
!
P̂R2 Ĵ
= + + Un (R) φn (R) (5.16)
2µ 2µR2
M1 M2
with the reduced mass µ = M1 +M2
.
• Simplest model: rigid rotor

The rigid rotor is defined by setting R = Re , i.e., by assuming that the
internuclear distance is held fixed at the equilibrium distance. In this
model, φn depend only on angular coordinates and Eq. (5.16) reduces
to
2
Ĵ
Erot φJM (θ, ϕ) = φJM (θ, ϕ) (5.17)
2µRe2
~2 J(J + 1) ~2 J(J + 1)
Erot = = J = 0, 1, . . .(5.18)
2µRe2 2I
2
I = µRe moment of inertia (5.19)
φJM (θ, ϕ) = YJM (θ, ϕ) (5.20)
Measurement of rotational absorption spectra (typically in the mi-

crowave regime) give information on I, i.e., on Re .
75
• Allow for radial motion: vibrations

Equation (5.16) can be separated by using the ansatz
PnJ (R)
φn (R) = YJM (θ, ϕ)
R
֒→ radial equation:
2 2
~ d ~2 J (J + 1)
− + Un (R) + PnJ (R) = EPnJ (R) (5.21)
2µ dR2 2µR2
• Taylor-expand bonding ground-state PES about equilibrium distance:

1
U0 (R) ≈ U0 (Re ) + U0′ (Re )(R − Re ) + U0′′ (Re )(R − Re )2 + ...
2
ke 2
= U0 (Re ) + x (5.22)
2
with
ke = U0′′ (Re ) molecular force constant

x = R − Re
use this to obtain the approximate radial equation

~2 ′′ 1 2 ~2 J(J + 1)
− PnJ (x) + ke x PnJ (x) = E − U0 (R) − PnJ (x)
2µ 2 2µRe2
≡ Evib PnJ (x) (5.23)
which is the SE of the harmonic oscillator with eigenenergies

1
Evib = ~ωe ν + ν = 0, 1, 2, ...
2
s s
ke U0′′ (Re )
and ωe = =
µ µ
76
E
Re
R
De D0 D1
U0 (R)
Figure 5.2: Typical ground-state PES and harmonic oscillator model of vi-
brational motion. De = U0 (Re ) is the binding energy and D0 = De − ~ω2 e the
dissociation energy of the molecule.
Summary:
E = U0 (Re ) + Evib + Erot
with
Eel = U0 (Re ) = E0 (Re ) + ∆0 (Re )

1
Evib = ~ωe ν +
2
2
~ J(J + 1)
Erot =
2I
note that
• E0 (Re ) is independent of µ
• Evib ∝ √1
µ
1
• Erot ∝ µ
• ֒→ Erot ≪ Evib ≪ Eel
Literature: [Lev], Chaps. 4.3 and 6.4; [Hur], Chap. 1

77
5.3 The hydrogen molecular ion H+

2
The hydrogen molecular ion is the simplest molecular system and plays a
similar role in molecular physics as the hydrogen atom in atomic physics.
The electronic SE can be solved exactly (but not in closed analytical form).
Let’s just take a look (without going into technical details).
The electronic SE (atomic units)

1 2 1 1 1
− ∇ − − + Ψn (r, R) = En (R)Ψn (r, R) (5.24)
2 ra rb R
is separable in confocal-elliptical coordinates (ξ, η, ϕ):

1
ξ = (ra + rb ) 1 ≤ ξ < ∞
R
1
η = (ra − rb ) − 1 ≤ η ≤ 1
R
y
ϕ = arctan 0 ≤ ϕ < 2π
x
with the standard azimuthal angle ϕ:
Ψ(ξ, η, ϕ) = M(ξ)N(η)φ(ϕ) (5.25)

for Φ(ϕ) one obtains

d2 2
+ λ φ(ϕ) = 0
dϕ2
⇒ φ(ϕ) = eiλϕ
require uniqueness:
φ(ϕ) = φ(ϕ + 2π)

iλ2π iλϕ
= e|{z} e ⇒ λ = 0, ±1, ±2, ...
1
∂
֒→ ˆlz φλ (ϕ) = −i φλ (ϕ) = λφλ (ϕ)
∂ϕ
h i
ˆ
⇒ Ĥ, lz = 0
78
However: h i
2
Ĥ, l̂ 6= 0
⇒ use λ to classify states
H atom l = 0 1 2 3
notation s p d f
+
H2 λ = 0 ±1 ±2 ±3
notation σ π δ ϕ
Table 5.1: Classification of atomic vs. molecular one-electron states
Eigenfunctions Ψ(ξ, η, ϕ) of Eq. (5.25) are also parity eigenstates

∢ point reflections:

 ξ → ξ
r → −r =⇒ η → −η

ϕ → ϕ+π
→ two types of solutions
ψ(r) = ψ(ξ, η, ϕ)
= ψ(ξ, −η, ϕ + π)
= ψ(−r)
= ψg (r) gerade (even) parity
ψ(r) = ψ(ξ, η, ϕ)
= −ψ(ξ, −η, ϕ + π)
= −ψ(−r)
= ψu (r) ungerade (odd) parity
→ classification of molecular orbitals (MOs)
1σg , 1σu , 2σg , 2σu , 3σg , 3σu , . . .

1πg , 1πu , 2πg , 2πu , 3πg , 3πu , . . .
..
.
79
1
Discussion of exact PESs En (R) and ”correlation diagrams” Enel (R) = En (R) − R
Note that
2
Enel (R → 0) = − ”united-atom limit”
n2
1
Enel (R → ∞) = − 2 ”separated-atom limit”
2n
Since the Enel are continuous functions of R, each united-atom state (e.g.
1sσg ) is correlated with a separated-atom state (e.g. σg (1s)).
Figure 5.3: Calculated correlation diagram (left) and PESs (right) of H+

2
80
σg (1s)
σ u (1s)
σg (1s) + σ u (1s)
Figure 5.4: Sketch of the electron density distributions of the lowest states
of gerade and ungerade parity in the separated-atom limit and how they add
to form an atomic state, e.g., on the left centre
Enel (R → 0) AO MO AO Enel (R → ∞)
-2.0 1s 1σg 1s -0.5
-0.5 2p0 1σu 1s -0.5
-0.5 2p1 1πu 2p1 -0.125
-0.5 2s 2σg 2s -0.125
-0.222 3p0 2σu 2s -0.125
-0.222 3d0 3σg 2p0 -0.125
-0.222 3d1 1πg 2p1 -0.125
-0.222 3d2 1δg 3d2 -0.056
-0.222 3p1 3πu 3p1 -0.056
-0.222 3s 4σg 3s -0.056
-0.125 4f0 3σu 2p0 -0.125
Table 5.2: Energies (in atomic units) and united- and separated-atom limits
of a few MOs of H+2
81
bond length Re 1.9972

E0 (Re ) -0.6026
E0el (Re ) -1.1033
binding energy De -0.1026
Table 5.3: Ground state properties of H+

2
Literature: [Lev], Chap. 13

Bibliography
[BD] Bjørken, J.D. and Drell, S.D.: Relativistic Quantum Mechanics.

McGraw-Hill.
[Boh] Bohm, D.: Quantum Theory. Prentice Hall.
[BS] Bethe, H. A. and Salpeter, E. E.: Quantum Mechanics of one-

and two-electron atoms. Plenum.
[CT] Cohen-Tannoudji, C.: Quantum Mechanics I, II. Wiley Inter-

science.
[Fri] Friedrich, H.: Theoretical Atomic Physics. Springer.
[GPS] Goldstein, H., C. Poole and J. Safko: Classical Mechanics.

Addison Wesley.
[Gri] Griffiths, D. J.: Introduction to Quantum Mechanics. Prentice

Hall.
[Hur] Hurley, A. C.: Introduction to the Electron Theory of Small

Molecules. Academic Press.
[Jac] Jackson, J. D.: Classical Electrodynamics. John Wiley & Sons.
[Lev] Levine, I. N.: Quantum Chemistry. Prentice Hall.
[Lib] Liboff, R. L.: Introductory Quantum Mechanics. Addison-Wesley.
[Mes] Messiah, A.: Quantum Mechanics I, II. Dover Publications.
[Sch] Schiff, L. L.: Quantum Mechanics. McGraw-Hill.
[Sha] Shankar, R.: Principles of Qunatum Mechanics. Kluwer Academic.
82
83
[SN] Sakurai, J. J. and J. Napolitano: Modern Quantum Mechanics.

Addison-Wesley.

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PHYS 4011, 5050:

Atomic and Molecular Physics

Department of Physics and Astronomy

1 Introduction: the field-free Schrödinger hydrogen atom 2

2 Atoms in electric fields: the Stark effect 16

3 Interaction of atoms with radiation 29

4 Brief introduction to relativistic QM 58

Introduction: the field-free

The starting point of the discussion is the stationary Schrödinger equation

1.1 Reduction to an effective one-body prob-

P̂2 p̂2  −Ze2 

֒→ Schrödinger equations (SEs)

Equation (1.7) can be solved analytically, but before we sketch the

1.2 The central-field problem for the relative

This is a manifestation of angular momentum conservation. In particular,

[Ĥrel , l̂2 ] = [Ĥrel , ˆlz ] = [l̂2 , ˆlz ] = 0 (1.11)

֒→ ansatz ϕrel (r) = Rl (r)Ylm (θ, ϕ) . (1.12)

Useful definition : yl (r) = rRl (r) (1.14)

1.3 Solution of the Coulomb problem

(square integrable solutions required)

2. Erel > 0 (continuous spectrum)

֒→ radial Eq. (1.15):

This consideration motivates the following ansatz

The square integrable solution of (1.20) (’Kummer’s’ or ’Laplace’s’ differen-

֒→ ynl (r) = Anl r l+1e−κn r Ln−l−1

and properly normalized wave functions take the form

The quantization condition (1.21) yields

The lowest-lying hydrogen eigenfunctions (’orbitals’):

n l m nr = n − l − 1 ϕnlm (r) −En

Figure 1.1: Energy spectrum of the Schrödinger-Coulomb problem. Note that

Degeneracy of energies (which depend only on n)

−→ each energy level En is n2 -fold degenerate. Note that all central-field

ρnlm (r) = |ϕnlm(r)|2 = Rnl

with p = ~k and the spherical Bessel functions jL .

Probability densities can be defined in the same way as in coordinate space

ρnlm (p) = |ϕnlm (p)|2

The maximum of the 2p probability density is shifted to smaller r com-

The number of nodes in momentum space and coordinate space is the

(and vice versa). This phenomenon is related to the uncertainty principle.

Check the Maple file hydrogen.mw for more details!

1.4 Assorted remarks

(a) positronium (e+ e− )

• measure mass in units of me

In other words, atomic units (a.u.) are defined by setting me = e =

• length: let’s look at Bohr’s radius

• energy: let’s look at the hydrogen ground state H(1s)

• time: let’s do a dimensional analysis

distance distance × mass distance2 × mass

Atoms in electric fields: the

What happens if we place an atom in a uniform electric field? One observes

2.1 Stationary perturbation theory for non-

Ĥ|ϕα i = Eα |ϕα i (2.6)

Ĥ0 |ϕ0α i = Eα(0) |ϕ0α i, hϕ0α |ϕ0β i = δαβ (2.8)

Ŵ ≡ λŵ with λ ≪ 1 (2.9)

We need to find expressions for the derivatives in Eqs. (2.11), (2.12):

hϕβ (λ)|ŵ|ϕα (λ)i

hϕα (λ)|ϕ′α (λ)i = 0

Let’s also consider the 2nd derivative term in Eq. (2.11):

Higher order terms can be calculated by differentiating expressions (2.15),

P̂2 p̂2 −Ze2