Introduction to Spectroscopy –IV,

B.Sc. III Year

Dr. Kishor Arora
Prof.- Chemistry,
Govt. Postgraduate College (Auto.);
Datia (M.P.)
 This presentation contains

• Set of Assignment/ Set of questions on

“Introduction of Spectroscopy”
 Assignment/ set of questions
Q1. Write a note on rotator.
Q2. Explain criteria for a molecule to be IR active
Q3. Explain selection rules.
Q4. What do you understand by electromagnetic
spectrum.
Q5. State and explain Beer- Lambert’s Law.
Q6.Which of the following will be IR active:
Water ,carbon di oxide, ethylene, ammonia,
hydrochloric acid, carbon mono oxide
And why
Assignment / Set of questions (Cont’d)
• Q7. Explain instrumentation of IR spectroscopy.
• Q8. Explain the types of vibrations
• Q9. Explain application of IR spectroscopy in the
structural elucidation of molecule
• Q10. Explain Theory of Vibration- Rotation
Spectroscopy.
• Q11. Explain the application of IR spectroscopy in
determination of force constant
• Q12. Explain Application of IR/ Microwave
spectroscopy in the determination of bond length.
Assignment/ Set of Questions (Cont’d)
• Q13. What is isotopic effect.
• Q14. Explain the theory of microwave
spectroscopy.
• Q15. Explain the estimation of moment of inertia
and bond length.
• Q16. What is the condition of a molecule to be
microwave active?
• Q17. Explain selection rules for microwave
spectroscopy.
• Q18. What do you understand by PQR barnches ?
Assignment/ Set of Questions (Cont’d)
• Q19. Explain basic principle of NMR spectroscopy
• Q20. What is chemical shift?
• Q21. What do you understand by Iso bestic
point?
• Q22. What is nuclear shielding?
• Q23. What do you understand by nuclear spin.?
• Q24. Explain the instrumentation used in NMR
spectroscopy.
Assignment/ Set of Questions (Cont’d)
• Q25.What do you understand by electronic
transitions?
• Q26. Explain solvent effect.
• Q27. Explain the effect of conjugation on
electronic transition.
• Q28. What is charge transfer spectra?
• Q29. What is the principle of electronic
spectroscopy?
• Q30. Explain Franck Condon Rule.
 Assignment/ Set of questions (cont’d)
• Q31. Explain the terms:- Red shift, Blue shift,
hypsochromic shift, batho chromic shift.
• Q32.Explain the terms : Fluorescence,
Phosphorescence
• Q33. Draw and explain Jablonski diagram.
• Q34. Explain the terms: dissociation, pre- dissociation
• Q35. Explain the instrumentation used in UV –visible
spectroscopy.
• Q36. Explain the applications of electronic
spectroscopy
Assignment/ Set of Questions (Cont’d)
• Q37.Explain Raman Effect.
• Q38. Write a note on quantum theory of Raman
effect.
• Q39. Write a note on classical theory of Raman
effect.
• Q40. Explain the origin of stroke’s and anti-
stroke’s lines.
• Q41. Explain the applications of Raman
spectroscopy.
• Q42. Explain Rotation Raman Spectroscopy.
• Best of Luck
Introduction To Spectroscopy,
Part – II, B.Sc. III year, Paper-I
Dr. Kishor Arora
Professor- Chemistry
Govt. Postgraduate College (Autonomous);
Datia (M.P.)- 475661
 This lecture Includes
• IR spectroscopy
Introduction
Features
Selection Rule/ Normal modes
Types of Vibrations
IR spectrophotometers
A typical IR Spectrum
Applications of IR spectroscopy
• NMR spectroscopy
Introduction
Magnetic Moment and Gyro Magnetic Ratio
Principle
Orientation of Spins
Distribution of Energy Levels
Frequency of Absorption
Nuclear Shielding
A typical NMR Spectrum
Relaxation
Applications of NMR
 IR Spectroscopy
• Introduction
• Infrared spectroscopy (IR spectroscopy) is
the spectroscopy that deals with the infrared region of
the electromagnetic spectrum, that is light with a
longer wavelength and lower frequency than visible
light.
• It covers a range of techniques, mostly based
on absorption spectroscopy.
• it can be used to identify and study chemicals.
• For a given sample which may be solid, liquid, or
gaseous, the method or technique of infrared
spectroscopy uses an instrument called an infrared
spectrometer
 IR Spectroscopy
• Features
• The infrared portion of the electromagnetic spectrum is
usually divided into three regions; the near-, mid- and far-
infrared, named for their relation to the visible spectrum.
• The higher-energy near-IR, approximately 14000–
4000 cm−1 (0.8–2.5 μm wavelength) can
excite overtone or harmonic vibrations.
• The mid-infrared, approximately 4000–400 cm−1 (2.5–
25 μm) may be used to study the fundamental vibrations
and associated rotational-vibrational structure.
• The far-infrared, approximately 400–10 cm−1 (25–1000 μm),
lying adjacent to the microwave region, has low energy and
may be used for rotational spectroscopy.
 IR Spectroscopy
• Selection Rules/ Normal Modes
• In the Born–Oppenheimer and harmonic approximations,
i.e. when the molecular Hamiltonian corresponding to the
electronic ground state can be approximated by a harmonic
oscillator in the neighborhood of the equilibrium molecular
geometry, the resonant frequencies are associated with
the normal modes corresponding to the molecular
electronic ground state potential energy surface.
• The resonant frequencies are also related to the strength of
the bond and the mass of the atoms at either end of it.
Thus, the frequency of the vibrations are associated with a
particular normal mode of motion and a particular bond
type.
 Types of Vibrations

Symmetrical Antisymmetrical
Scissoring
stretching stretching

Rocking Wagging Twisting

IR Spectrophotometer
A typical IR Spectrum
Applications of IR Spectrophotometer
 Applications of IR Spectroscopy
• Infrared spectroscopy is a simple and reliable
technique widely used in both organic and inorganic
chemistry, in research and industry. It is used in quality
control, dynamic measurement, and monitoring
applications such as the long-term unattended
measurement of CO2 concentrations in greenhouses
and growth chambers by infrared gas analyzers.
• It is also used in forensic analysis in both criminal and
civil cases, for example in identifying polymer
degradation. It can be used in determining the blood
alcohol content of a suspected drunk driver.
 Applications of IR Spectroscopy
• A useful way of analysing solid samples without the
need for cutting samples uses ATR or attenuated total
reflectancespectroscopy. Using this approach, samples
are pressed against the face of a single crystal. The
infrared radiation passes through the crystal and only
interacts with the sample at the interface between the
two materials.
• With increasing technology in computer filtering and
manipulation of the results, samples in solution can
now be measured accurately (water produces a broad
absorbance across the range of interest, and thus
renders the spectra unreadable without this computer
treatment).
 Applications of IR Spectroscopy
• Infrared spectroscopy is also useful in measuring the degree of
polymerization in polymer manufacture. Changes in the character
or quantity of a particular bond are assessed by measuring at a
specific frequency over time. Modern research instruments can
take infrared measurements across the range of interest as
frequently as 32 times a second. This can be done whilst
simultaneous measurements are made using other techniques. This
makes the observations of chemical reactions and processes
quicker and more accurate.
• Infrared spectroscopy has also been successfully utilized in the field
of semiconductor microelectronics:[for example, infrared
spectroscopy can be applied to semiconductors like silicon, gallium
arsenide, gallium nitride, zinc selenide, amorphous silicon, silicon
nitride, etc.
• The instruments are now small, and can be transported, even for
use in field trials.
 NMR Spectroscopy
• Introduction
• Nuclear Magnetic Resonance (NMR) is a nuclei (Nuclear)
specific spectroscopy that has far reaching applications
throughout the physical sciences and industry.
• NMR uses a large magnet (Magnetic) to probe the intrinsic
spin properties of atomic nuclei. Like all spectroscopies,
NMR uses a component of electromagnetic radiation (radio
frequency waves) to promote transitions between nuclear
energy levels (Resonance).
• Most chemists use NMR for structure determination of
small molecules.
 NMR Spectroscopy
• In 1946, NMR was co-discovered by Purcell,
Pound and Torrey of Harvard University and
Bloch, Hansen and Packard of Stanford University.
• The discovery first came about when it was
noticed that magnetic nuclei, such as 1H and 31P
(proton and Phosphorus 31) were able to absorb
radio frequency energy when placed in a
magnetic field of a strength that was specific to
the nucleus.
 NMR Spectroscopy
• Upon absorption, the nuclei begin to resonate
and different atoms within a molecule
resonated at different frequencies.
• This observation allowed a detailed analysis of
the structure of a molecule.
• Since then, NMR has been applied to solids,
liquids and gasses, kinetic and structural
studies, resulting in 6 Nobel prizes being
awarded in the field of NMR.
 Magnetic Moment & Gyro magnetic
Ratio
• All molecules with a non-zero spin have a
magnetic moment, μ, given by
• μ=γI
• where γ is the gyro magnetic ratio, a
proportionality constant between the
magnetic dipole moment and the angular
momentum, specific to each nucleus.
 Gyromagnetic Ratio
Nuclei Spin Gyromagetic Ratio Natural Abundance
(MHz/T) (%)
1
H 1/2 42.576 99.9985
13
C 1/2 10.705 1.07
31
P 1/2 17.235 100
27
Al 5/2 11.103 100
23
Na 3/2 11.262 100
7
Li 3/2 16.546 92.41
29
Si 1/2 -8.465 4.68
17
O 5/2 5.772 0.038
15
N 1/2 -4.361 0.368
 Principle
• The magnetic moment of the nucleus forces the
nucleus to behave as a tiny bar magnet.
• In the absence of an external magnetic field,
each magnet is randomly oriented.
• During the NMR experiment the sample is placed
in an external magnetic field, B0, which forces the
bar magnets to align with (low energy) or against
(high energy) the B0.
• During the NMR experiment, a spin flip of the
magnets occurs, requiring an exact quanta of
energy.
Orientation of Spins
 Distribution in Energy Levels
• An exact quanta of energy must be used to induce the spin flip or
transition. For any m, there are 2m+1 energy levels. For a spin 1/2
nucleus, there are only two energy levels, the low energy level
occupied by the spins which aligned with B0 and the high energy
level occupied by spins aligned against B0. Each energy level is given
by
E=−mℏγB0
where m is the magnetic quantum number, in this case +/- 1/2.
• The energy levels for m>1/2, known as quadrupolar nuclei, are
more complex and information regarding them can be found here.
• The energy difference between the energy levels is then
ΔE=ℏγB0
• where ℏ is Planks constant.
Energy Levels
 Frequency for absorption
• For most NMR spectrometers, B0 is on the
order of Tesla (T) while γ is on the order
of 107. Consequently, the electromagnetic
radiation required is on the order of Hz. The
energy of a photon is represented by
E=hν
• and thus the frequency necessary for
absorption to occur is represented as:
ν=γB02π
Frequency of Absorption
 Nuclear Shielding

• The power of NMR is based on the concept of nuclear

shielding, which allows for structural assignments.
• Every atom is surrounded by electrons, which orbit the
nucleus.
• Charged particles moving in a loop will create a
magnetic field which is felt by the nucleus.
• Therefore the local electronic environment
surrounding the nucleus will slightly change the
magnetic field experienced by the nucleus, which in
turn will cause slight changes in the energy levels! This
is known as shielding.
 Nuclear Shielding

• Nuclei that experinece differnet magnetic

fields due to the local electronic interactions
are known as inequivalent nuclei.
• The change in the energy levels requires a
different frequency to excite the spin flip,
which as will be seen below, creates a new
peak in the NMR spectrum.
Nuclear Shielding
A Typical NMR Spectrum
 Relaxation
• Relaxation refers to the phenomenon of nuclei
returning to their thermodynamically stable
states after being excited to higher energy levels.
• The energy absorbed when a transition from a
lower energy level to a high energy level occurs is
released when the opposite happens.
• This can be a fairly complex process based on
different timescales of the relaxation.
• The two most common types of relaxation
are spin lattice relaxation (T1) and spin spin
relaxation (T2).
Relaxation
 Relaxation
• To understand relaxation, the entire sample
must be considered.
• By placing rhe nuclei in an external magnetic
field, the nuclei create a bulk magnetization
along the z-axis.
• The spins of the nuclei are also coherent. The
NMR signal may be detected as long as the
spins are coherent with one another
 Applications
• Medicine
Nuclear magnetic resonance imaging, better known as magnetic
resonance imaging (MRI) is an important medical diagnostic tool used to
study the function and structure of the human body. It provides detailed
images of any part of the body, especially soft tissue, in all possible planes
and has been used in the areas of cardiovascular, neurological,
musculoskeletal and oncological imaging.
 Application
• Chemistry
In many laboratories today, chemists use nuclear
magnetic resonance to determine structures of
important chemical and biological compounds.

In NMR spectra, different peaks give information about

different atoms in a molecule according specific
chemical environments and bonding between atoms.

The most common isotopes used to detect NMR

signals are 1H and 13C but there are many others, such
as 2H,3He, 15N, 19F, etc., that are also in use
 Application
• Other Fields
• NMR has also proven to be very useful in other area
such as environmental testing, petroleum industry,
process control, earth’s field NMR and magnetometers.

Non-destructive testing saves a lot of money for

expensive biological samples and can be used again if
more trials need to be run.

The petroleum industry uses NMR equipment to

measure porosity of different rocks and permeability of
different underground fluids.
• Best of Luck
Introduction to spectroscopy,
Part –III, B.Sc. III year
Dr. Kishor Arora
Professor- Chemistry,
Govt. Postgraduate College, (Auto.);
Datia (M.P.) 475 661
 This Presentation Contains
• UV –Visible Spectroscopy
– Introduction – Applications
– It’s Principle – Instrumentation
– Electronic Transitions • Raman Spectroscopy-
– Solvent Effect  Raman Effect
– Effect of conjugation
 Rayleigh Scattering
– Charge Transfer Spectra
– Franck Condon Principle  Quantum Theory of Raman Effect
– Basic Laws  Classical Theory Of Raman Effect
– Some terms related to UV-Visible  Stroke’s and Anti-Stroke’s Lines
Spectroscopy
 Selection Rules
– Dissociation and Pre-dissociation
– Fluorescence and phosphorescence  Rotation Raman Spectra
– Jablonski Diagram  Applications

 Introduction
• Ultraviolet–visible spectroscopy or ultraviolet–visible
spectrophotometry (UV–Vis or UV/Vis) refers to absorption
spectroscopy or reflectance spectroscopy in part of
the ultraviolet and the full, adjacent visible spectral regions.
• This means it uses light in the visible and adjacent ranges. The
absorption or reflectance in the visible range directly affects the
perceived color of the chemicals involved.
• In this region of the electromagnetic
spectrum, atoms and molecules undergo electronic transitions.
Absorption spectroscopy is complementary to fluorescence
spectroscopy, in that fluorescence deals with transitions from
the excited state to the ground state, while absorption measures
transitions from the ground state to the excited state.
Introduction-Electronic Spectra origin
 Principle
• Molecules containing bonding and non-bonding electrons
(n-electrons) can absorb energy in the form of ultraviolet or
visible light to excite these electrons to higher anti-bonding
molecular orbitals.
• The more easily excited the electrons (i.e. lower energy
gap between the HOMO and the LUMO), the longer the
wavelength of light it can absorb.
• There are four possible types of transitions viz.
• π–π*,
• n–π*,
• σ–σ*, and
• n–σ*,
• These can be ordered as follows :σ–σ* > n–σ* > π–π* > n–π
Electronic Transitions
 Electronic Transitions
• s ® s* Transitions
An electron in a bonding s orbital is excited to the corresponding antibonding
orbital. The energy required is large. For example, methane (which has only C-H
bonds, and can only undergo s ® s* transitions) shows an absorbance maximum at
125 nm. Absorption maxima due to s ® s* transitions are not seen in typical UV-Vis.
spectra (200 - 700 nm)
• n ® s* Transitions
Saturated compounds containing atoms with lone pairs (non-bonding electrons)
are capable of n ® s* transitions. These transitions usually need less energy than s ®
s * transitions. They can be initiated by light whose wavelength is in the range 150 -
250 nm. The number of organic functional groups with n ® s* peaks in the UV
region is small.
• n ® p* and p ® p* Transitions
Most absorption spectroscopy of organic compounds is based on transitions
of n or p electrons to the p* excited state. This is because the absorption peaks for
these transitions fall in an experimentally convenient region of the spectrum (200 -
700 nm). These transitions need an unsaturated group in the molecule to provide
the p electrons.
• Molar absorbtivities from n ® p* transitions are relatively low, and range from 10
to100 L mol-1 cm-1 . p ® p* transitions normally give molar absorbtivities between
1000 and 10,000 L mol-1 cm-1 .
{where s =σ ; p = π and n= non bonding orbitals]
 Electronic Transitions (Appearance in
Compounds)
σ→σ* Alkanes

σ→π* Carbonyl compounds

π →π* Alkenes, carbonyl compn, alkyne etc.
n→σ* Oxygen, nitrogen, sulfur and halogen
compounds
n →π* Carbonyl compounds (Usually
Forbodden)
 Solvent Effect
• The solvent in which the absorbing species is dissolved also
has an effect on the spectrum of the species. Peaks
resulting from n p* transitions are shifted to shorter
wavelengths (blue shift) with increasing solvent polarity.
This arises from increased solvation of the lone pair, which
lowers the energy of the n orbital. Often (but not always),
the reverse (i.e. red shift) is seen for p p* transitions. This is
caused by attractive polarisation forces between the
solvent and the absorber, which lower the energy levels of
both the excited and unexcited states. This effect is greater
for the excited state, and so the energy difference between
the excited and unexcited states is slightly reduced -
resulting in a small red shift. This effect also
influences n p* transitions but is overshadowed by the blue
shift resulting from solvation of lone pairs.
 Effect of conjugation
• Increase in conjugation decreases the energy
gap between π and π* orbitals, as a result of
which π →π* transition shifts towards lower
wavelength side.
• Shown in the next slide
Effect of conjugation
 Charge Transfer Spectra
• Many inorganic species show charge-transfer
absorption and are called charge-transfer complexes.
For a complex to demonstrate charge-transfer
behaviour, one of its components must have electron
donating properties and another component must be
able to accept electrons. Absorption of radiation then
involves the transfer of an electron from the donor to
an orbital associated with the acceptor.
• Molar absorbtivities from charge-transfer absorption
are large (greater that 10,000 L mol-1 cm-1).
 Franck –Condon Principle
• The Franck–Condon principle is a rule
in spectroscopy and quantum chemistry that
explains the intensity of vibronic transitions.
Vibronic transitions are the simultaneous changes
in electronic and vibrational energy levels of a
molecule due to the absorption or emission of
a photon of the appropriate energy. The principle
states that during an electronic transition, a
change from one vibrational energy level to
another will be more likely to happen if the two
vibrational wave functions overlap more
significantly.
Franck Condon Principle
Basic Laws of UV- Visible Spectroscopy
Basic Law {c=νλ}
 Some important terms related to
Electronic Spectra
Bathochromic shift (red shift): a shift to lower
energy or longer wavelength.
Hypsochromic shift (blue shift): a shift to higher
energy or shorter wavelength.
Hyperchromic effect: An increase in intensity.
Hypochromic effect: A decrease in intensity.
 Dissociation and Pre- dissociation
• If excitation transfers a molecule in a state containing more energy than the separated
components (atoms, or molecules), dissociation takes place. Above the dissociation
limit the energy is not quantized and energy continuum appears instead of discrete
energy levels. The dissociative state is not stable, which means that the molecule
disassembled into the separated components very quickly (approximately during the
time of one vibration).In some spectra the discrete energy level structure disappears
already for energies which are below the dissociation limit but reappears again at some
higher energies. This phenomenon is called predissociation.
• Predissociation can be usually explained as a result of internal conversion from an
excited state A into a dissociative state B. We assume relationship between the
vibrational states closely above the level of intersection and the translational motion
during dissociation. These circumstances allow a separation of a molecule via state B
without supplying the energy of dissociation for state A. Note that, in the range beyond
the blurred caused by predissociation, discrete lines are found. An interpretation would
be that for higher vibrational states, a conversion towards state B is excluded again.
• Sometimes, predissociation is a result of some additional external factors. For example,
we can imagine a molecule to be pushed from state A to state B due to collision with
another atom, or molecule. Alternatively, an external electric, or magnetic field can
cause to the predissociation of an initially stable molecule. In such cases, we speak
of collision- or field- induced predissociation.
•
Dissociation and Pre- dissociation
 Fluorescence and phosphorescence
• Fluorescence and phosphorescence are types of molecular
luminescence methods. A molecule of analyte absorbs a
photon and excites a species. The emission spectrum can
provide qualitative and quantitative analysis. The term
fluorescence and phosphorescence are usually referred as
photoluminescence because both are alike in excitation
brought by absorption of a photon. Fluorescence differs from
phosphorescence in that the electronic energy transition that
is responsible for fluorescence does not change in electron
spin, which results in short-live electrons (<10-5 s) in the
excited state of fluorescence. In phosphorescence, there is a
change in electron spin, which results in a longer lifetime of
the excited state (second to minutes). Fluorescence and
phosphorescence occurs at longer wavelength than the
excitation radiation.
Fluorescence and phosphorescence
 Jablonski Diagram
• The Jablonski diagram that drawn below is a
partial energy diagram that represents the energy
of photoluminescent molecule in its different
energy states. The lowest and darkest horizontal
line represents the ground-state electronic
energy of the molecule which is the singlet state
labeled as So. At room temperature, majority of
the molecules in a solution are in this state.
Jablonski Diagram
 Applications of UV Visible
Spectroscopy
• UV/Vis spectroscopy is routinely used in analytical chemistry for
the quantitative determination of different analytes, such as transition metal ions,
highly conjugated organic compounds, and biological macromolecules. Spectroscopic analysis
is commonly carried out in solutions but solids and gases may also be studied.
• Solutions of transition metal ions can be colored (i.e., absorb visible light) because d
electrons within the metal atoms can be excited from one electronic state to another. The
colour of metal ion solutions is strongly affected by the presence of other species, such as
certain anions or ligands. For instance, the colour of a dilute solution of copper sulfate is a
very light blue; adding ammonia intensifies the colour and changes the wavelength of
maximum absorption (λmax).
• Organic compounds, especially those with a high degree of conjugation, also absorb light in
the UV or visible regions of the electromagnetic spectrum. The solvents for these
determinations are often water for water-soluble compounds, or ethanol for organic-soluble
compounds. (Organic solvents may have significant UV absorption; not all solvents are
suitable for use in UV spectroscopy. Ethanol absorbs very weakly at most wavelengths.)
Solvent polarity and pH can affect the absorption spectrum of an organic compound.
Tyrosine, for example, increases in absorption maxima and molar extinction coefficient when
pH increases from 6 to 13 or when solvent polarity decreases.
• While charge transfer complexes also give rise to colours, the colours are often too intense to
be used for quantitative measurement.
 Instrumentation
• The basic parts of a spectrophotometer are a light source, a holder for the sample,
a diffraction grating in a monochromator or a prism to separate the different
wavelengths of light, and a detector. The radiation source is often a Tungsten filament
(300–2500 nm), a deuterium arc lamp, which is continuous over the ultraviolet region
(190–400 nm), Xenon arc lamp, which is continuous from 160 to 2,000 nm; or more
recently, light emitting diodes (LED)[ for the visible wavelengths. The detector is
typically a photomultiplier tube, a photodiode, a photodiode array or a charge-coupled
device (CCD). Single photodiode detectors and photomultiplier tubes are used with
scanning monochromators, which filter the light so that only light of a single
wavelength reaches the detector at one time. The scanning monochromator moves the
diffraction grating to "step-through" each wavelength so that its intensity may be
measured as a function of wavelength. Fixed monochromators are used with CCDs and
photodiode arrays. As both of these devices consist of many detectors grouped into one
or two dimensional arrays, they are able to collect light of different wavelengths on
different pixels or groups of pixels simultaneously.
• Simplified schematic of a double beam UV–visible spectrophotometer
• A spectrophotometer can be either single beam or double beam. In a single beam
instrument (such as the Spectronic 20), all of the light passes through the sample
cell. Initial intensity must be measured by removing the sample. This was the earliest
design and is still in common use in both teaching and industrial labs.
Instrumentation
 Raman Spectrocopy
• Raman scattering or the Raman effect is the inelastic
scattering of photons by matter, meaning that there is an exchange
of energy and a change in the light's direction. Typically this
involves vibrational energy being gained by a molecule as incident
photons from a visible laser are shifted to lower energy. This is
called normal Stokes Raman scattering. The effect is exploited by
chemists and physicists to gain information about materials for a
variety of purposes by performing various forms of Raman
spectroscopy.
• Many other variants of Raman spectroscopy allow rotational
energy to be examined (if gas samples are used) and electronic
energy levels may be examined if an X-ray source is used in addition
to other possibilities.
• More complex techniques involving pulsed lasers, multiple laser
beams and so on are known.
 Rayleigh scattering
• Light has a certain probability of being scattered by a material. When photons
are scattered, most of them are elastically scattered (Rayleigh scattering), such
that the scattered photons have the same energy (frequency, wavelength and
color) as the incident photons but different direction. Rayleigh scattering
usually has an intensity in the range 0.1% to 0.01% relative to that of a
radiation source. An even smaller fraction of the scattered photons
(approximately 1 in 10 million) can be scattered in-elastically, with the
scattered photons having an energy different (usually lower) from those of the
incident photons—these are Raman scattered photons. Because
of conservation of energy, the material either gains or loses energy in the
process.
• Rayleigh scattering was discovered and explained in the 19th century. The
Raman effect is named after Indian scientist C. V. Raman, who discovered it in
1928 with assistance from his student K. S. Krishnan. Raman was awarded the
Nobel prize in Physics in 1930 for his discovery although Grigory
Landsberg and Leonid Mandelstam observed the effect in crystals the same
year as Raman. The effect had been predicted theoretically by Adolf Smekal in
1923
Quantum Theory of Raman Effect
Stroke’s and Anti-Stroke’s Lines
 Selection Rules
• In contrast to IR spectroscopy, where there is a requirement for a change in dipole moment
for vibrational excitation to take place, Raman scattering requires a change in polarizability. A
Raman transition from one state to another is allowed only if the molecular polarizability of
those states is different. For a vibration, this means that the derivative of the polarizability
with respect to the normal coordinate associated to the vibration is non-zero: In general, a
normal mode is Raman active if it transforms with the same symmetry of the quadratic which
can be verified from the character table of the molecule's point group. As with IR
spectroscopy, only fundamental are allowed according to the QHO. There are however many
cases where overtones are observed.
• The rule of mutual exclusion, which states that vibrational modes cannot be both IR and
Raman active, applies to certain molecules.
• The specific selection rules state that the allowed rotational transitions are , where there is
the rotational state. This generally is only relevant to molecules in the gas phase where the
Raman linewidths are small enough for rotational transitions to be resolved.
• A selection rule relevant only to ordered solid materials states that only phonons with zero
phase angle can be observed by IR and Raman, except when phonon confinement is
manifest.
 Rotation Raman Spectra
• Molecular rotational transitions can also be observed
by Raman spectroscopy. Rotational transitions are Raman-
allowed for any molecule with
an anisotropic polarizability which includes all molecules
except for spherical tops. This means that rotational
transitions of molecules with no permanent dipole
moment, which cannot be observed in absorption or
emission, can be observed, by scattering, in Raman
spectroscopy. Very high resolution Raman spectra can be
obtained by adapting a Fourier Transform Infrared
Spectrometer. An example is the spectrum of 15N
2. It shows the effect of nuclear spin, resulting in intensities
variation of 3:1 in adjacent lines. A bond length of 109.9985
± 0.0010 pm was deduced from the data.
 Applications
• Raman spectroscopy employs the Raman effect for substances analysis. The spectrum
of the Raman-scattered light depends on the molecular constituents present and their
state, allowing the spectrum to be used for material identification and analysis. Raman
spectroscopy is used to analyze a wide range of materials, including gases, liquids, and
solids. Highly complex materials such as biological organisms and human tissue can also
be analyzed by Raman spectroscopy.
• For solid materials, Raman scattering is used as a tool to detect high-frequency phonon
and magnon excitations.
• Raman lidar is used in atmospheric physics to measure the atmospheric extinction
coefficient and the water vapour vertical distribution.
• Stimulated Raman transitions are also widely used for manipulating a trapped ion's
energy levels, and thus basis qubit states.
• Raman spectroscopy can be used to determine the force constant and bond length for
molecules that do not have an infrared absorption spectrum.
• Raman amplification is used in optical amplifiers.
• The Raman effect is also involved in producing the appearance of the blue sky
(see Rayleigh Scattering: 'Rayleigh scattering of molecular nitrogen and oxygen in the
atmosphere includes elastic scattering as well as the inelastic contribution from
rotational Raman scattering in air').
 References
• “Rasaynik Spectroscopy”, O.P. Srivastava and
Kishor Arora, M.P. Hindi Granth Academy
publication.
• Chemistry B.Sc. Part - III, Shivlal Agarwal and
Company.
• Wikipedia
• Best Of Luck
Introduction to Spectroscopy
B.Sc. III year Paper –I, Part I
Kishor Arora
Professor-Chemistry,
Govt. P.G. College (Auto.) ; Datia (M.P.) -
475661
 This Lecture Includes
• Introduction to spectroscopy
• Wave nature of light
• Electromagnetic spectrum
• Colorimetery
• Spectrophotometers / spectroscopes
• Instrumentation
• A typical spectrum
• Beer- Lambart’s Law/ Absorbance and transmittance
• Isobestic Point
• Selection Rule (In General)
 Introduction
• Spectro-photometry is a method to measure
how much a chemical substance absorbs light
by measuring the intensity of light as a beam
of light passes through sample solution.
• The basic principle is that each compound
absorbs or transmits light over a certain range
of wavelength.
• This measurement can also be used to
measure the amount of a known chemical
substance.
 Introduction
• Spectro-photometry is one of the most useful
methods of quantitative analysis in various fields
such as chemistry, physics, biochemistry, material
and chemical engineering and clinical
applications.
• Spectro-photometry is widely used for
quantitative analysis in various areas (e.g.,
chemistry, physics, biology, biochemistry, material
and chemical engineering, clinical applications,
industrial applications, etc).
 Introduction
• Any application that deals with chemical
substances or materials can use this
technique. In biochemistry, for example, it is
used to determine enzyme-catalyzed
reactions.
• In clinical applications, it is used to examine
blood or tissues for clinical diagnosis.
 Introduction
• There are also several variations of the
spectro-photometry such as atomic
absorption spectro-photometry and atomic
emission spectro-photometry.
 Wave Nature of Light
• Electromagnetic radiation moves in waves
Electromagnetic Spectrum
VIBGYOR
 Electromagnetic Spectrum
COLOR WAVELENGTH (λ in nm)
Ultraviolet < 380
Violet 380 – 435
Blue 436 – 480
Greenish-blue 481 – 490
Bluish-green 491 – 500
Green 501 – 560
Yellowish-green 561 – 580
Yellow 581 – 595
Orange 596 – 650
Red 651 – 780
Near Infrared > 780
 Colorimetery
• The solutions of many compounds have
characteristic colors.

• The intensity of such a color is proportional to

the concentration of the compound.
Spectroscopes Vs. Spectrophotometers
• Light can either be transmitted or absorbed by
dissolved substances

• Presence & concentration of dissolved substances is

analyzed by passing light through the sample

• Spectroscopes measure electromagnetic emission

• Spectrophotometers measure electromagnetic

absorption
 Instrumentation
• What do visible spectrophotometers
measure?
– Amount of light absorbed by the dissolved
substance

– Qualitative
– Quantitative
 Instrumentation
• A spectrophotometer is an instrument that
measures the amount of photons (the intensity of
light) absorbed after it passes through sample
solution.
• With the spectrophotometer, the amount of a
known chemical substance (concentrations) can
also be determined by measuring the intensity of
light detected.
• Depending on the range of wavelength of light
source, it can be classified into two different
types:
 Instrumentation
• UV-visible spectrophotometer: uses light over
the ultraviolet range (185 - 400 nm) and
visible range (400 - 700 nm) of
electromagnetic radiation spectrum.
• IR spectrophotometer: uses light over the
infrared range (700 - 15000 nm) of
electromagnetic radiation spectrum.
 Instrumentation
• Spectrometer: It produces a desired range of
wavelength of light. First a collimator (lens) transmits a
straight beam of light (photons) that passes through a
monochromator (prism) to split it into several
component wavelengths (spectrum). Then a
wavelength selector (slit) transmits only the desired
wavelengths.
• Photometer: After the desired range of wavelength of
light passes through the solution of a sample in
cuvette, the photometer detects the amount of
photons that is absorbed and then sends a signal to a
galvanometer or a digital display.
Block Diagram
Instrument
A typical Spectrum
 Beer- Lambart Law
• Beer-Lambert Law (also known as Beer's Law) states that
there is a linear relationship between the absorbance and
the concentration of a sample. For this reason, Beer's Law
can only be applied when there is a linear relationship.
Beer's Law is written as:
• A=ϵlc
where
A is the measure of absorbance (no units),
ϵ is the molar extinction coefficient or molar absorptivity
(or absorption coefficient),
 Beer Lambart Law
l is the path length, and
c is the concentration.
• The molar extinction coefficient is given as a
constant and varies for each molecule. Since
absorbance does not carry any units, the units
for ϵ must cancel out the units of length and
concentration. As a result,
• ϵ has the units: L·mol-1·cm-1.
Beer Lambart Law
 Absorbance Vs. Transmittance
• Transmittance is the fraction of light that
passes through the sample. This can be
calculated using the equation:
• Transmittance(T)=ItIo
• Transmittance is related to absorption by the
expression:
• Absorbance(A)=−log(T)=−log(ItIo)
 Isobestic Point
• An isosbestic point is the wavelength in which
the absorbance of two or more species are the
same. The appearance of an isosbestic point in
a reaction demonstrates that an intermediate
is NOT required to form a product from a
reactan
Isobestic Point
 Selection Rules (In General)
• In physics and chemistry, a selection rule, or transition
rule, formally constrains the possible transitions of a
system from one quantum state to another. Selection
rules have been derived for electromagnetic transitions
in molecules, in atoms, in atomic nuclei, and so on. The
selection rules may differ according to the technique
used to observe the transition. The selection rule also
plays a role in chemical reactions, where some are
formally spin-forbidden reactions, that is, reactions
where the spin state changes at least once
from reactants to products.
 Selection Rules (In General)
• In quantum mechanics the basis for a
spectroscopic selection rule is the value of the
transition moment integral
 Selection Rules (In General)
• Where these are the wave functions of the two states
involved in the transition and µ is the transition
moment operator
• This integral represents the propagator (and thus the
probability) of the transition between states; therefore
if the value of this integral is zero then the transition is
forbidden.
• If the symmetry of this function spans the totally
symmetric representation of the point group to which
the atom or molecule belongs then its value is (in
general) not zero and the transition is allowed.
Otherwise, the transition is forbidden.
 Selection Rules (In General)
• Symmetry characteristics of transition moment
operator. Following table shows transition type
along with dipole moment operator and type of
spectra
Transition type µ transforms as note
Electric dipole x, y, z Optical spectra
Constraint x2 + y2 +
Electric quadrupole x2, y2, z2, xy, xz, yz
z2 = 0
Electric
x2, y2, z2, xy, xz, yz Raman spectra
polarizability
Optical spectra
Magnetic dipole Rx, Ry, Rz
(weak)
• Best Of Luck
Photo Chemistry, B.Sc. III Year,
Paper --I
Dr. Kishor Arora
Professor- Chemistry,
Govt. Postgraduate College, (Auto.);
Datia (M.P.) 475 661
 This presentation Contains
• Photo chemical reactions- • Sensitizers
Introduction • Actinometers
• Differences between • Norrish type 1 and 2 Reactions
Photochemical and thermal • Assignment and Set of
reactions questions
• Basic Laws of Photochemistry
 Grothous Drapper’s Law
 Stark Einstein’s Law
 Beer Lambert’s law
• Quantum Yield
• Low and high quantum yield
• Fluorescence and Phosphoresce
• Jablonski Diagram
• Photo- sensitization
 Introduction
• Photochemistry is the branch
of chemistry concerned with the chemical
effects of light. Generally, this term is used to
describe a chemical reaction caused by
absorption of ultraviolet (wavelength from
100 to 400 nm), visible light (400–750 nm)
or infrared radiation (750–2500 nm).
 Introduction
• In nature, photochemistry is of immense importance as
it is the basis of photosynthesis, vision, and the
formation of vitamin D with sunlight.
• Photochemical reactions proceed differently than
temperature-driven reactions.
• Photochemical paths access high energy intermediates
that cannot be generated thermally, thereby
overcoming large activation barriers in a short period
of time, and allowing reactions otherwise inaccessible
by thermal processes.
• Photochemistry is also destructive, as illustrated by
the photodegradation of plastics.
 Basic Laws of Photo Chemistry
(Grothous Draper’s Law)
• The Grotthuss–Draper law (also called the Principle of
Photochemical Activation) states that only that light which
is absorbed by a system can bring about a photochemical
change. Materials such as dyes and phosphors must be able
to absorb "light" at optical frequencies.
• This law provides a basis
for fluorescence and phosphorescence.
• The law was first proposed in 1817 by Theodor
Grotthuss and in 1842, independently, by John William
Draper.[5]
• This is considered to be one of the two basic laws
of photochemistry.
 Basic Laws of Photochemistry
(Stark- Einstein’s Law)
• The Stark–Einstein law is named after German-born physicists Johannes
Stark and Albert Einstein, who independently formulated the law between
1908 and 1913. It is also known as the photochemical equivalence
law or photoequivalence law. In essence it says that every photon that is
absorbed will cause a (primary) chemical or physical reaction.
• The photon is a quantum of radiation, or one unit of radiation. Therefore,
this is a single unit of EM radiation that is equal to Planck's constant (h)
times the frequency of light. This quantity is symbolized by γ, hν, or ħω.
• The photochemical equivalence law is also restated as follows: for
every mole of a substance that reacts, an equivalent mole of quanta of
light are absorbed.
• The formula is:Δ E= NA hν
• where NA is Avogadro's number.
 Basic Laws of Photochemistry
(Stark- Einstein’s Law)
• The photochemical equivalence law applies to the part of a light-
induced reaction that is referred to as the primary process
(i.e. absorption or fluorescence).
• In most photochemical reactions the primary process is usually
followed by so-called secondary photochemical processes that are
normal interactions between reactants not requiring absorption of
light. As a result, such reactions do not appear to obey the one
quantum–one molecule reactant relationship.
• The law is further restricted to conventional photochemical
processes using light sources with moderate intensities; high-
intensity light sources such as those used in flash photolysis and in
laser experiments are known to cause so-called biphotonic
processes; i.e., the absorption by a molecule of a substance of two
photons of light.
 Quantum yield
• The quantum yield (Φ) of a radiation-induced
process is the number of times a specific
event occurs per photon absorbed by the
system. The "event" is typically a kind
of chemical reaction.
 Quantum yield
• The quantum yield for the decomposition of a
reactant molecule in a decomposition reaction is
defined as:
(Φ) = (No. of molecules decomposed)/ (No. of
photons absorbed)
• Quantum yield can also be defined for other
events, such as fluorescence:
(Φ) = (Photons emitted)/ Photons absorbed)
• Here, quantum yield is the emission efficiency of
a given fluorophore.
 Low and High Quantum yield
• High Quantum Yield : When two or more
molecules are decomposed per photon,
the quantum yield ϕ > 1 and the reaction has
a high quantum yield.
• Low Quantum Yield : When the number of
molecules decomposed is less than one per
photon, the quantum yield ϕ < 1 and the
reaction has a low quantum yield.
Basic Laws of Photochemistry
 Fluorescence and phosphorescence
• Fluorescence and phosphorescence are types of molecular
luminescence methods. A molecule of analyte absorbs a
photon and excites a species. The emission spectrum can
provide qualitative and quantitative analysis. The term
fluorescence and phosphorescence are usually referred as
photoluminescence because both are alike in excitation
brought by absorption of a photon. Fluorescence differs from
phosphorescence in that the electronic energy transition that
is responsible for fluorescence does not change in electron
spin, which results in short-live electrons (<10-5 s) in the
excited state of fluorescence. In phosphorescence, there is a
change in electron spin, which results in a longer lifetime of
the excited state (second to minutes). Fluorescence and
phosphorescence occurs at longer wavelength than the
excitation radiation.
Fluorescence and phosphorescence
 Jablonski Diagram
• The Jablonski diagram that drawn below is a
partial energy diagram that represents the energy
of photoluminescent molecule in its different
energy states. The lowest and darkest horizontal
line represents the ground-state electronic
energy of the molecule which is the singlet state
labeled as So. At room temperature, majority of
the molecules in a solution are in this state.
Jablonski Diagram
 Photo Sensitization
• Photosensitization is a process of transferring the energy of absorbed light.
After absorption, the energy is transferred to the (chosen) reactants. This is
part of the work of photochemistry in general. In particular this process is
commonly employed where reactions require light sources of
certain wavelengths that are not readily available.
• For example, mercury absorbs radiation at 1849 and 2537 angstroms, and the
source is often high-intensity mercury lamps. It is a commonly used sensitizer.
When mercury vapor is mixed with ethylene, and the compound
is irradiated with a mercury lamp, this results in the photodecomposition of
ethylene to acetylene. This occurs on absorption of light to yield excited state
mercury atoms, which are able to transfer this energy to the ethylene
molecules, and are in turn deactivated to their initial energy state.
• Cadmium; some of the noble gases, for example xenon; zinc; benzophenone;
and a large number of organic dyes, are also used as sensitizers.
• Photosensitisers are a key component of photodynamic therapy used to treat
cancers.
 Sensitizer
• A sensitizer in chemiluminescence is a chemical compound, capable of light emission after it has received
energy from a molecule, which became excited previously in the chemical reaction. A good example is this:
• When an alkaline solution of sodium hypochlorite and a concentrated solution of hydrogen peroxide are
mixed, a reaction occurs:
• ClO−(aq) + H2O2(aq) → O2*(g) + H+(aq) + Cl−(aq) + OH−(aq)O2*is excited oxygen – meaning, one or more
electrons in the O2 molecule have been promoted to higher-energy molecular orbitals. Hence, oxygen
produced by this chemical reaction somehow 'absorbed' the energy released by the reaction and became
excited. This energy state is unstable, therefore it will return to the ground state by lowering its energy. It
can do that in more than one way:
• it can react further, without any light emission
• it can lose energy without emission, for example, giving off heat to the surroundings or transferring energy
to another molecule
• it can emit light
• The intensity, duration and color of emitted light depend on quantum and kinetical factors. However,
excited molecules are frequently less capable of light emission in terms of brightness and duration when
compared to sensitizers. This is because sensitizers can store energy (that is, be excited) for longer periods
of time than other excited molecules. The energy is stored through means of quantum vibration, so
sensitizers are usually compounds which either include systems of aromatic rings or many conjugated
double and triple bonds in their structure. Hence, if an excited molecule transfers its energy to a sensitizer
thus exciting it, longer and easier to quantify light emission is often observed.
• The color (that is, the wavelength), brightness and duration of emission depend upon the sensitizer used.
Usually, for a certain chemical reaction, many different sensitizers can be used.
 Actinometers
• Actinometers are instruments used to measure the
heating power of radiation. They are used
in meteorology to measure solar
radiation as pyranometers, pyrheliometers and net
radiometers.
• An actinometer is a chemical system or physical device
which determines the number of photons in a beam
integrally or per unit time. This name is commonly applied
to devices used in the ultraviolet and visible wavelength
ranges. For example, solutions of iron(III) oxalate can be
used as a chemical actinometer,
while bolometers, thermopiles, and photodiodes are
physical devices giving a reading that can be correlated to
the number of photons detected.
 Norrish Type 1 and 2 Reactions
• The Norrish reaction in organic
chemistry describes the photochemical
reactions taking place
with ketones and aldehydes.
• This type of reaction is subdivided in Norrish
type I reactions and Norrish type II reactions.
• The reaction is named after Ronald George
Wreyford Norrish.
 Norrish type I reaction
• The Norrish type I reaction is the photochemical cleavage
or homolysis of aldehydes and ketones into two free
radical intermediates. The carbonyl group accepts a photon
and is excited to a photochemical singlet state.
Through intersystem crossing the triplet state can be
obtained. On cleavage of the α-carbon bond from either
state, two radical fragments are obtained. The size and
nature of these fragments depends upon the stability of the
generated radicals; for instance, the cleavage of 2-
butanone largely yields ethyl radicals in favor of less stable
methyl radicals.
•
Norrish type 1 reaction
 Norrish type 1 reaction
• Several secondary reaction modes are open to these fragments depending
on the exact molecular structure.
• The fragments can simply recombine to the original carbonyl compound,
with racemisation at the α-carbon.
• The acyl radical can lose a molecule of carbon monoxide, forming a new
carbon radical at the other α-carbon, followed by formation of a new
carbon–carbon bond between the radicals.The ultimate effect is simple
extraction of the carbonyl unit from the carbon chain. The rate and yield
of this product depends upon the bond-dissociation energy of the
ketone's α substituents. Typically the more α substituted a ketone is, the
more likely the reaction will yield products in this way.
• The abstraction of an α-proton from the carbonyl fragment may form
a ketene and an alkane.
• The abstraction of a β-proton from the alkyl fragment may form
an aldehyde and an alkene.
Norrish type 1 Reaction
 Norrish Type 2 Reaction
• A Norrish type II reaction is the
photochemical intramolecular abstraction of
a γ-hydrogen (a hydrogen atom three carbon
positions removed from the carbonyl group)
by the excited carbonyl compound to produce
a 1,4-biradical as a primary photoproduct.
Norrish first reported the reaction in 1937.
Norrish type 2 Reaction
 Assignment and set of questions
• Q1. What do you understand by photochemistry?
• Q2. What are the types of photo chemical
reactions?
• Q3.What are the differences between
photochemical and thermal reactions?
• Q4.State and explain Grothous Draper’s law
• Q5. State and explain Stark’s Einstien’s law.
• Q6. What do you understand by quantum yield?
 Assignment and set of questions
• Q7. Explain low and high quantum yield.
• Q8. State and explain Beer Lambert's Law
• Q9. Differentiate between fluorescence and
phosphorescence
• Q10. What do you understand by internal
conversion and intersystem crossing?
• Q11. Draw and explain Jablonski diagram.
• Q12.
 Assignment and set of questions
• Q13 What is photo sensitization? Write a note
on sensitizers.
• Q14.What are actinometers?
• Q15.Write short note on :
 Norrish type 1 reaction and
 Norrish type 2 reaction
• Best of Luck
Physical properties and Molecular
Structure, B.Sc. III year, Paper I
Dr. Kishor Arora,
Professor- Chemistry,
Govt. Postgraduate College, (Datia );
M.P. – 475 661
 This Presentation Includes
• Optical activity
• Polari meter
• Measuring Optical Activity: Enantiomers
• Optical Activity: Areas of Use
• Clausius–Mossotti equation
• Lorentz–Lorenz equation
• Dipole Moment
• Dipole Moment: Examples
• Dipole Moment: Formula
• Debye Equation
• Magnetic Moment
• Magnetic Susceptibility
• Types of Magnetic materials
 Optical Activity
• Optical activity is the ability of a chiral molecule to rotate
the plane of plane-polairsed light, measured using
a polarimeter.
• A simple polarimeter consists of a light source, polarising
lens, sample tube and analysing lens.
• When light passes through a sample that can rotate plane
polarised light, the light appears to dim because it no
longer passes straight through the polarising filters. The
amount of rotation is quantified as the number of degrees
that the analysing lens must be rotated by so that it
appears as if no dimming of the light has occurred.
Optical Activity: Polari meter
 Measuring Optical Activity
• When rotation is quantified using a polarimeter it
is known as an observed rotation, because
rotation is affected by path length (l, the time the
light travels through a sample) and concentration
(c, how much of the sample is present that will
rotate the light). When these effects are
eliminated a standard for comparison of all
molecules is obtained, the specific rotation, [α].
• [α] = 100 α / cl when concentration is
expressed as g sample /100ml solution
 Optical Activity: Enantiomers
• Enantiomers will rotate the plane of polarization in
exactly equal amounts (same magnitude) but in
opposite directions.
• Dextrorotary designated as d or (+), clockwise rotation
(to the right)
Levorotary designated as l or (-), anti-clockwise
rotation (to the left)If only one enantiomer is present a
sample is considered to be optically pure.
• When a sample consists of a mixture of enantiomers,
the effect of each enantiomer cancels out, molecule for
molecule.
 Optical Activity: Areas of use

• For a pure substance in solution, if the color and path

length are fixed and the specific rotation is known, the
observed rotation can be used to calculate the
concentration. This usage makes a polar meter a tool of
great importance to those trading in or using sugar
syrups in bulk.
• In the presence of an applied magnetic field, it is
possible for samples of all compounds to exhibit optical
activity. A magnetic field aligned in the direction of
light propagating through a material will cause the
rotation of the plane of linear polarization.
This Faraday effect is one of the first discoveries of the
relationship between light and electromagnetic effects.
 Clausius–Mossotti equation

• The Clausius–Mossotti relation expresses

the dielectric constant (relative permittivity,
εr) of a material in terms of the atomic
polarizibility, α, of the material's constituent
atoms and/or molecules, or a homogeneous
mixture thereof. It is named after Ottaviano-
Fabrizio Mossotti and Rudolf Clausius. It is
equivalent to the Lorentz–Lorenz equation. It
may be expressed as:
 Lorentz–Lorenz equation

• The Lorentz–Lorenz equation is similar to the

Clausius–Mossotti relation, except that it
relates the refractive index (rather than
the dielectric constant) of a substance to
its polarizability. The Lorentz–Lorenz equation
is named after the Danish mathematician and
scientist Ludvig Lorenz, who published it in
1869, and the Dutch physicist Hendrik Lorentz,
who discovered it independently in 1878.
Lorentz–Lorenz equation
 Dipole moment
• A dipole moment arises in any system in which
there is a separation of charge. They can,
therefore, arise in ionic bonds as well as in
covalent bonds. Dipole moments occur due to
the difference in electronegativity between two
chemically bonded atoms.
• A bond dipole moment is a measure of the
polarity of a chemical bond between two atoms
in a molecule. It involves the concept of electric
dipole moment, which is a measure of the
separation of negative and positive charges in a
system.
 Dipole Moment
• The bond dipole moment is a vector quantity
since it has both magnitude and direction. An
illustration describing the dipole moment that
arises in an HCl (hydrochloric acid) molecule is
provided below
 Dipole Moment
• Important Points
• The dipole moment of a single bond in a polyatomic molecule is known as
the bond dipole moment and it is different from the dipole moment of the
molecule as a whole.
• It is a vector quantity, i.e. it has magnitude as well as definite directions.
• Being a vector quantity, it can also be zero as the two oppositely acting
bond dipoles can cancel each other.
• By convention, it is denoted by a small arrow with its tail on the negative
center and its head on the positive center.
• In chemistry, the dipole moment is represented by a slight variation of the
arrow symbol. It is denoted by a cross on the positive center and
arrowhead on the negative center. This arrow symbolizes the shift of
electron density in the molecule.
• In the case of a polyatomic molecule, the dipole moment of the molecule
is the vector sum of the all present bond dipoles in the molecule.
 Dipole Moment Formula
• A dipole moment is the product of the magnitude of the charge and
the distance between the centers of the positive and negative
charges. It is denoted by the Greek letter ‘µ’.
• Mathematically,
• Dipole Moment (µ) = Charge (Q) * distance of separation (r)
• It is measured in Debye units denoted by ‘D’. 1 D = 3.33564 × 10-
30 C.m, where C is Coulomb and m denotes a meter.

• The bond dipole moment that arises in a chemical bond between

two atoms of different electronegativities can be expressed as
follows:
• μ = 𝛿.d
• Where: μ is the bond dipole moment,
• 𝛿 is the magnitude of the partial charges 𝛿+ and 𝛿–,
• And d is the distance between 𝛿+ and 𝛿–.
 Dipole Moment
• The bond dipole moment (μ) is also a vector
quantity, whose direction is parallel to the bond
axis. In chemistry, the arrows that are drawn in
order to represent dipole moments begin at the
positive charge and end at the negative charge.
• When two atoms of varying electronegativities
interact, the electrons tend to move from their
initial positions to come closer to the more
electronegative atom. This movement of
electrons can be represented via the bond dipole
moment.
 Example: Dipole moment of BeF2
• In a beryllium fluoride molecule, the bond
angle between the two beryllium-fluorine
bonds is 180o. Fluorine, being the more
electronegative atom, shifts the electron
density towards itself. The individual bond
dipole moments in a BeF2 molecule are
illustrated below.
 Example: Dipole moment of H2O (Water)
• In a water molecule, the electrons are
localized around the oxygen atom since it is
much more electronegative than the hydrogen
atom. However, the presence of a lone pair of
electrons in the oxygen atom causes the water
molecule to have a bent shape (as per
the VSEPR theory). Therefore, the individual
bond dipole moments do not cancel each
other out as is the case in the BeF2 molecule.
An illustration describing the dipole moment
in a water molecule is provided below.
 Example: Dipole moment of H2O
(Water)

The bond angle in a water molecule is 104.5o. The individual bond moment of
an oxygen-hydrogen bond is 1.5 D. The net dipole moment in a water
molecule is found to be 1.84D
More Examples: Dipole Moment
More Examples : Dipole Moment
Measurement of Dipole Moment :Relative
Permittivity, Polarization, and Polarizability
Debye Equation
Magnetic Moment
 Magnetic Susceptibility
• Magnetic susceptibility is a dimensionless proportionality constant that indicates the
degree of magnetization of a material in response to an applied magnetic field. It is
caused by interactions of electrons and nuclei with the externally applied magnetic
field.
• What is Magnetic Susceptibility?
• In electromagnetism, magnetic susceptibility is defined as:
• The measures of how much a material will be magnetized in an applied magnetic field.
• It is denoted by χ.
• Magnetic Susceptibility Formula
• The mathematical definition of magnetic susceptibility is the ratio of magnetization to
applied magnetizing field intensity. This is a dimensionless quantity.
• χ=M/H
• Where,
• χ: magnetic susceptibility
• M: magnetization
• H: field intensity
 Types of Magnetic Materials

• With the help of magnetic susceptibility, magnetic

materials can be classified as:
• Paramagnetic material: Magnetic materials which
align with the magnetic field are known as
paramagnetic materials. Magnetic susceptibility is χ>0
which means it is always a small positive value for
paramagnetic materials. These materials are
temperature dependent and are weekly attracted by
magnets with relative permeability 1.00001 to 1.003.
Alkaline earth metal, aluminium, oxygen etc are some
of the examples of paramagnetic materials.
 Types of Magnetic Materials
• Diamagnetic material: Magnetic materials which align
against the magnetic field are known as diamagnetic
materials. Magnetic susceptibility is χ<0 which means it
is always a negative value for diamagnetic material.
These materials are repelled by the magnets and they
move from a stronger field to a weaker field. These
materials are independent of temperature. As these
materials magnetize in the opposite direction, they do
have a small amount of magnetization intensity. Gold,
tin, mercury, water, etc are examples of diamagnetic
materials. Diamagnetic materials have a constant
relative permeability.
 Types of Magnetic Materials
• Ferromagnetic material: Magnetic materials that
are highly magnetized in a magnetic field are
known as ferromagnetic materials. These are
highly attracted by the magnets and move from
weaker fields to stronger fields. Ferromagnetic
materials do not have a constant relative
permeability and vary from 1000 to 100000.
Magnetic susceptibility is very high and positive
and depends on the applied field. Iron, cobalt,
nickel and their alloys are examples of
ferromagnetic materials.
 Assignment/ Set of Questions
• Q1. What do you understand by optical activity?
• Q2.What are Enantiomers?
• Q3. Explain the construction of polar meter
• Q4. Define optical activity and its areas of uses.
• Q5.Write and explain Clausius–Mossotti equation
• Q6. Write and explain Lorentz–Lorenz equation.
• Q7. What do you understand by Dipole Moment?
• Q8. What is the formula for dipole moment? What is
its unit?
• Q9. How can you correlate dipole moment with the
structure of any compound.
 Assignment / Set of Questions
Q10. Which of the following molecules will have the
permanent dipole moment and why?
Water, boron tri flouride, carbon mono oxide, carbon di
oxide, ammonia, sulfur tri oxide, benzene, m- di nitro
benzene
Q11.Explain the measurement of dipole moment.
Q12. What do you understand by magnetic moment?
Q13. What is magnetic susceptibility?
Q14. Write and Explain Debye equation.
Q15. Write a note on the following: (i) Diamagnetism (ii)
paramagnetism (iii) Ferromagnetism
• Best of Luck