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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.

com

2014

MCH-107:

SPECTROSCOPY-I

UNIT-I:

ATOMIC SPECTROSCOPY
The electromagnetic spectrum, A general discussion on various molecular
excitation processes, Spectra of hydrogen and hydrogen like atoms, alkali metals
spectra, L-S coupling, Term symbols, Space quantisation, Zeeman effect, Stark
effect, Paschen-Back effect.

UNIT-II:

VIBRATIONAL AND ROTATIONAL SPECTROSCOPY


Molecular Spectra of Diatomic Gases, Classification of molecules, Rotational
Spectra, Vibrational Spectra, Vibrational-Rotational Spectra, P, Q and R Branches
RAMAN SPECTROSCOPY
Theory of Raman spectra, Rotational Raman spectra, Vibrational Raman spectra,
Rotational-Vibrational Raman spectra, comparison with IR spectra.

UNIT-III:

4 Credits

BOOKS:
1. Text Book of Physical Chemistry Vol-1-4 : K.L. Kapoor
2. Physical Chemistry
: D.N. Bajpai
3. Physical Chemistry
: A.W. Atkins
4. Physical Chemistry Through Problems
: Dogra & Dogra
5. Physical Chemistry Principles & Problems : Jain & Jabuhar
6. Statistical Thermodynamics
: M. C. Gupta
7. Fundamentals of Statistical Mechanics
: B.B. Laud
8. Spectroscopy Vol. I & II
: Walker & Straw
9. Fundamentals of Molecular Spectroscopy : C.N. Banwell
10. Fundamentals of Molecular Spectroscopy : G.M. Barrow
Unit-I
The electromagnetic spectrum, A general discussion on various molecular excitation processes.
SPECTROSCOPY
Introduction:
Significance of spectroscopy:
The determination of molecular structure has been a central problem in chemistry. Many
methods using electromagnetic radiations have been developed to understand and to elucidate the
molecular structure. These are spectroscopic methods and provide molecular spectra.
OH
C4H10O
Exact Mass: 74.07

O
C4H10O
Exact Mass: 74.07

O
C4H10O
Exact Mass: 74.07

The study of molecular spectra provides valuable


information regarding the structure of molecules,
arrangement and presence of various groups,
internuclear distance (bond lengths, bond angles),
geometry of molecules, etc.

VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

In order to obtain molecular spectra the matter is exposed to electromagnetic radiations and
the resulting change in e.m radiation results spectrum.
DEFINITION:
SPECTROSCOPY: Spectroscopy is both detection and analysis of the interacted electromagnetic
radiation with the matter.
OR
Spectroscopic data is often represented by a spectrum, a plot of the response of interest as a
function of wavelength or frequency or wave number.
SPECTRUM:
The record of spectral intensity as a function of
frequency () or Wavelength () of the radiation emitted or
absorbed by an atom or a molecule is called its spectrum.
The equivalent word of Spectrum in Greek is
appearance. It consists of a series of lines or sharply
defined emission or absorption peaks.

Intensity

Frequency

APPLICATION:
It gives the proof in determining the structure of molecule considered.
Advantages of spectroscopy:
1. Spectroscopic methods are much more rapid and much less time consuming.
2. They give information which is recorded in the form of a permanent chart generally in an
automatic or semi-automatic manner.
3. They require very small amount (at mg and g levels) of the compound even this amount can be
recovered at the end of examination in many cases.
4. The structural information gained by spectroscopic methods is much more precise and reliable;
they are highly reliable in establishing the identity of two compounds.
5. They are much selective and sensitive and are extremely valuable in the analysis of highly
complex mixtures and in the detection of even trace amounts of impurities.
6. In general the sample can be recycled.
7. With these methods, continuous operation is often possible and this facilitates automatic control of
process variables in industry.

VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

GENERATION OF ELECTROMAGNETIC RADIATION (EMR):


When an electric charge is rotated within a magnetic field or a magnet is rotated within an
electric field, electromagnetic radiation is produced which has an electric component and a magnetic
component perpendicular to each other and both these components are perpendicular to the direction
of propagation of the radiation.
Electromagnetic waves exist with an enormous range of frequencies. This continuous range
of frequencies is known as the electromagnetic spectrum. The entire range of the spectrum is often
broken into specific regions. The subdividing of the entire spectrum into smaller spectra is done
mostly on the basis of how each region of electromagnetic waves interacts with matter.

CHARACTERISTICS OF ELECTROMAGNETIC RADIATION:


1. EMR has electric and magnetic component perpendicular to each other.
2. It is not deflected by either electric field or by magnetic field.
3. It doesnt require any medium for its propagation.
4. All types Electromagnetic radiations have same velocity i.e., velocity of light 3x108ms-1, however
their energies and frequencies may be different.
Properties of matter:
Quantization of Energy:
Max Planck theory:
A Molecule in space can have many sorts of energy e.g., it may possesses rotational energy
by virtue of bodily rotation about its center of gravity; it will have vibrational energy due to periodic
displacement of its atom from their equilibrium positions; it will have electronic energy since the
electrons associated with each atom or bond are in unceasing motion, etc.

VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

The rotational, vibrational and other energies of a molecule are also quantized- a particular
molecule can either exist in a variety of rotational, vibrational, etc., energy levels and can move from
one level to another only by a sudden jump involving a finite amount of energy.
E2

E = E2 - E1

= Nh
E1
N = 6.02 X 10 23
Avagadro number
h = 6.63 X 10 -34 JSmolecule-1
Plancks constant

Transitions can take place between the levels E1 and E2


provided the appropriate amount of energy (E) can be either
absorbed or emitted by the system.
The spectroscopist measures the various characteristics of the
absorbed or emitted radiation during transitions between
energy states interms of wavenumber (cm-1) rather than Hz.

Mechanism of energy absorption


In all branches of chemistry three things are important. First the absorbing body and the
second is the electromagnetic radiation that is incident on the absorber, absorbed and then results in
an absorption spectrum which is detected by an instrument called spectrometer. The spectrometer
constitutes the third important thing. The absorbing body consists of molecules, atoms, electrons and
nuclei. Each of these individual things have different energy levels. All these energy levels are
quantized. If the molecule is in a lower energy level E1, it can be promoted to E2 providing the
frequency of radiation is such that E = h.

VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

n=3
J=5
J=4
J=3
J=2
J=1
J=0V=0
J=5

v=2

J=4
J=3
J=2
J=1
J=0

v=1

J=5
J=4
J=3
J=2
J=1
J = 0, V = 0
J=5

n=2

J=4
J=3

J=2
J=1
J = 0, V =
J0= 5

v=2

J=4
J=3

J=2
J=1
J = 0, V = 0

v=1

J=5
J=4
J=3

n=1
Electronic levels

J=2

J=1
Vibrational levels

Rotational levels

v=0
J=0

Electronicm vibrational and rotational energy levels in a diatomic molecule

In such a case, energy energy and amount of radiation absorbed is recorded by the
spectrometer and is presented in the form of a spectrum. Most often a spectrum results by plotting
intensity (I) or function of it against energy (E) of incident radiation.

VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

Intensity is defined as the number of photons of the incident radiation absorbed per unit area
of the absorber in unit time. The energy of radiation is usually replaced by wave length (, A0), wave
number (, cm-1), frequency (, Hz) or any other function related to it.

= h =

hc
= hc

Intensity

Frequency

A typical spectrum for absorption spectroscopy


The mechanism of energy absorption is varied depending on the nature of transition
involed.
REGIONS OF THE SPECTRUM:
Radiofrequency region (NMR + ESR spectroscopy) 3 x 106 - 3 x 1010 Hz: 10m- 1cm wavelength.
Energy associated with reversal spin of nucleus (nmr) or electron (esr) belongs to this region
and is of the order 0.001-10J/mole. The
Microwave region (Rotational spectroscopy or Microwave spectroscopy) 3 x 1010 - 3 x 1012 Hz:
1cm 100m wavelength.
Energy associated with the transition of molecules between various rotational energy levels
belong to this region. The separation between the rotational levels of molecules is of the order of
100J/mol.
Infrared region (Vibrational Spectroscopy) 3 x 1012 - 3 x 1014 Hz: 100m- 1m wavelength.
Energy associated with the transition of molecules between various vibrational energy levels
belong to this region. The separation between the vibrational levels of molecules is of the order of
10,000J/mol.
Visible of Ultra violet region (Electronic spectroscopy) 3 x 1014 - 3 x 1016 Hz: 1m- 10nm
wavelength.
Energy associated with the transition of molecules between various electronic energy levels
belong to this region. The separation between the electronic levels of molecules is of the order of
1lakhJ/mol.
X-Ray 3 x 1016 - 3 x 1018 Hz: 10nm - 100pm wavelength.

VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

Transitions involving the inner electrons of an atom or a molecule will takes place in this
region and it is of the order of 1 crore J/mole = 107 J/Mole.
-Ray 3 x 1016 - 3 x 1018 Hz: 100pm 1 pm wavelength.
The rearrangement of nuclear particles of an atom or molecule will takes place in this region
and it is of the order of 100 10,000 crore J/mole (109 1011J/Mol).
1. The radio frequency region: we may consider the nucleus and electron to be tiny charged
particles, and it follows their spin is associated with a tiny magnetic dipole. The reversal of this
dipole consequent upon the spin reversal which can interact with the magnetic field of
electromagnetic field of electromagnetic radiation at the appropriate frequency. Consequently all
such spin reversals produce an absorption or emission spectrum.
The amount of energy exactly needed to flip the
proton depends on the external field strength. The
stronger the field more becomes the frequency of
radiation needed to do the flipping.
H
=
2
= Frequency in Hz, H = strength of magnetic
fieldin gauss, = the gyromagnetic ratio, a
nuclear constant and has a calue of 26750 for a
proton

H
applied
magnetic
field

2. The microwave region:


Direction or
ratation

Vertical
component of
dipolemoment

Direction or
dipole
moment

Time

A molecule such as hydrogen chloride,


HCl, in which one atom (the hydrogen
atom) carries a permanent net positive
charge and the other a net negative charge,
is said to have a permanent electric dipole
moment. H2 and Cl2, on the other hand in
which there is no such charge separation,
have a zero dipole moment.

Wave length

Rotation of a polar diatomic moleculem shwoing the fluctuation in the


dipole moment moment measured in a particular direction

If we consider the rotation of HCl (notice that if only a pure rotation takes place, the centre of
gravity of the molecule must not move), the plus and minus charges change places periodically, and
the component dipole moment in a given direction (say upwards in the plane of the paper) fluctuates
regularly. This fluctuation is plotted in the lower half of the figure and it is seen to be exactly similar
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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

in form to the fluctuating electric field of radiation. Thus interaction can occur, energy can be
absorbed or emitted, and the rotation gives rise to a spectrum.
All molecules having a permanent dipole moment are said to be microwave active. If there is
no dipole, as in case of H2 or Cl2 no interaction can take place and the molecule is microwave
inactive. This imposes a limitation on the applicability of microwave spectroscopy.
3. The infra-red region:
Here it is a vibration, rather than a rotation; which must give rise to a dipole change. Consider
the carbon dioxide molecule as an example, in which the three atoms are arranged linearly with a
small net positive charge on the carbon and small negative charges on the oxygen.
O

+
C

+
C

O
O

+
C

Streched

Normal

Comprssed

Symmetric strtching vibration of the carbon dioxide molecule


with amplitude much exaggerated
Asymmetric
Stretching
Vibration

Direction or
dipole
moment

O
C

O
O

O
C

O
O

Vertical
component of
dipolemoment

During the mode of vibration known


as symmetric stretch, the molecule is
alternatively strtched and compressed,
both
C-O
bonds
changing
simultaneously. Plainly the dipole
moment remains zero throughout the
whole of this motion, and this
particular vibration is thus infrared
inactive.
In anti-symmetric stretch (or
asymmetric stretch), one bond
stretches while the other bond is
compressed, and vice versa. There is a
periodic alternation in the dipole
moment, and the vibration is thus
infrared active.

Time
Wave length

Wave length

Asymmetric stretching vibration of the carbon dioxide molecule


showing the fluctuation in the dipole moment

VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

Bending
Vibration

C
O

C
C

O
C

O
O

O
O

Direction or
dipole
moment

Vertical
component of
dipolemoment

Time
Wave length

Wave length

2014

Bending vibration is infrared


active. In neither of these motions
does the centre of gravity move. Note
particularly that the relative motions
of the atoms are very much
exaggerated, but in real molecules, the
displacement of atoms
during
vibration is seldom more than about
10% of the bond length.

Bending motion of the carbon dioxde molecule


and its associated dipole fluctuation

Although dipole change requirements do impose some limitation of the application of infrared spectroscopy, the appearance or non-appearance of certain vibration frequencies can give
valuable information about the structure of a particular molecule.
4. The visible and ultraviolet region: The excitation of a valance electron involves the moving of
electronic charges in the molecule. The consequent change in the electric dipole gives rise to a
spectrum by its interaction with the electric field of radiation.
5. Photelectron spectra (PES): PES offers one of the most accurate methods for determining the
ionization energies of molecules. Photoelectron spectra can be studied either using the X-ray
photons or UV photons. In the former case, they are called XPES spectra and in the latter case,
UVPES (or UPES) spectra. If the energy of the incident photon is greater than the ionization energy,
the ejected electron will possess excess kinetic energy. In PES, a beam of photons of known energy
is allowed to fall on the sample and the kinetic energy of the ejected electrons is measured. The
difference between the photon energy and the excess kinetic energy gives the binding energy of the
electron.
6. Mssbauer spectra (also called Nuclear Gamma resonance (NRF) spectra): Mssbauer
spectra constitute a type of nuclear resonance spectra like nuclear magnetic resonance spectra.
Mssbauer However, while NMR spectra result absorption of low energy photons of frequency
around 60MHz, Mssbauer spectra result from absorption of high energy photons of frequency
around 1013 MHz by the nuclei. ray spectra have been used specifically for the study of
compounds of iron and tin. In this case, radiations from 57Co source are allowed to fall on a sample
in which the iron nuclei are in an environment identical with that of the source atoms. This results
resonant absorption of rays. The splitting in Mssbauer lines are found to be of the same order as
in NMR spectroscopy.
The atomic spectra involve only transitions of electrons from one electronic level to another,
while molecular spectra involve transitions between rotational and vibrational energy levels, in

VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

addition to electronic transitions. Hence spectra of molecules are much more complicated than those
of atoms.
Line spectra or absorption spectra: An electron in the atom is raised from its normal or ground
state to some higher energy state, in one or more steps, energy is emitted in the form of line
spectrum. Line spectrum is, therefore, given by elements, by elements, characteristic of an element
and used to identify an element.Atoms produce line spectra, but molecules produce band spectra,
which have continuous bands caused by molecules and the band is made up of very closely spaced
lines. Since band spectra are caused by molecules, they are also known as molecular spectra. The
unit most commonly used for wave number is cm-1, sometimes called the Kaiser.
Ground states and excited states: the ground state of a molecule is that in which the molecule has
the lowest energy: other states are called excited states. At temperature T (0K) nearly all the
molecules will be in the ground state if the lowest excited state is appreciably more than (kT)/2
above the ground state. Here k is equal to R/N and is known as Boltzman constant.
If the molecule absorbs a photon of
energy h from the incident radiationby a
transition from mower state to excited
En state, then the resulting spectrum is called
absorption spectrum

Em
h

Em
h
En

If the molecule falls from the


excited state to the ground state
with the emission of energy of
h, the spectrum obtained is
called the emission spectrum

WIDTH OF SPECTRAL LINES

Transmittance

Detector
output

(a)

Frequency

Absorbance

Energy absorbed
by the sample

(b)

Frequency

The spectrum of a molecule undergoing a single transition:


(a) idealized, and (b) Usual appearance

The absorption and emission spectral lines are not always sharp lines but in many cases these
are broad lines. This may be due to the slits of the spectrometer, molecular collision, Doppler effect
and the uncertainty of energy in an energy state.

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

(i) Slits of the spectrometers: The width of the spectral line depends on the width of the slit of the
spectrometer. The narrower, the slit, the sharper is the spectrum.
(ii) Collision between the sample particles: This causes broadening of spectral lines particularly for
liquid samples. Since the molecules are atoms in the gas or liquid phase are in constant motion, they
collide with each other. The collision causes the deformity in the valence shell of these particles and
results in energy perturbation. Since different molecules collide to different extents, the energy
perturbation spreads over a range and results in a broad spectrum. This is particularly seen with
visible and ultraviolet spectroscopy which deals with electronic transition involving the valence
shell.
(iii) Doppler Effect: Molecules and atoms in the gaseous or liquid move randomly in all directions
and with different velocities. Depending on whether the absorbing particle moves towards or away
from the source of radiation, frequency addition or subtraction takes place. This is in turn broadens
the spectral line. Doppler broadening of spectra increases with the increase in temperature. Doppler
Effect often determines the natural line width.
(iv) Uncertainty principle: It is observed that the spectra of an isolated stationary molecule or atom
could not be sharp even if there is no other effect like collision of Doppler Effect. This is due to the
fact that whenever a system exists in an energy state for a very long period, T sec, the the energy of
that system would be uncertain to an extent of E. Hence according to the Heisenbergs uncertainity

principle, E X T
2
Where, h is Plancks constant having value 6.62 X 10-34 JSec. The ground state or the lower
energy state is very stable; therefore, the system will remain in the stable state for an infinite time.
For this state t = Infinity and E = 0. Bu the excited electronic state has lifetime of about 10 -8 Sec.

The transition between this state and the ground state will have a frequency uncertainity of , i.e.,

t
t

As mentioned above, the life time of an excited state is 10-8 sec and the uncertainity in frequency
1

will have value nearly (2)108 Hz. This large value of uncertainty is small as compared to the usual
radiation frequency of such transitions 3.7 X 1014-7.5 X 1014 Hz. Therefore, the peak width of
electronic spectra should be small, unless collision effect and Doppler Effect are simultaneously
experienced by the sample. But in case of an excited electron spin statem the life time is bout 10 -7
sec. So the frequency uncertainity is about 107 Hz. The usual transition frequency of such spin
transition frequency varies between 108 109 Hz. This causes a broad spectral line. Thus uncertainity
in energy is more important for the signal width in case of electron spin resonance spectroscopy.
Intensity of the spectral signals
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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

The intensity of spectral signals depends mainly on three factors:


(i) Transition probability:
(ii) Population of energy states and
(iii) The concentration and path length of the sample.
(i) Transition probability:
Let us consider transition between two energy states m and n of a system with corresponding
wave functions m and n. Then the lenear combination of m and n.
= Cmm(q,t) + Cnn(q,t), will also be a solution to the time dependent wave equation.
H(q,t) = i

(,)

where Cm and Cn are constants, q is the space coordinate and t is the time so that

is a function of both, H is the Hamiltonian operator and = 2.


When absorption of radiation causes transition from lower state to upper state (n), the hamiltonian is
replaced by H = H+H`
Where H` is the perturbation Hamiltonian and it represents the interaction between the electric field
() of the radiation and the electric field dipole moment () of the system.
H` = .

(H+H`)[ Cmm(q,t) + Cnn(q,t)] = i[ Cmm(q,t) + Cnn(q,t)]

H[ Cmm(q,t) + Cnn(q,t)] = i[

(,)

H`[ Cmm(q,t) + Cnn(q,t)] = i[ (, )

(,)

] and

+ (, )

This last equation is simplified to yield the transition probability:


2

2
Cn*(t)Cn(t) = |Cn|2 = 2
t,

where nm, transition dipole moment is given by

nm = () (x) dx.
It follows from equation that the transition from m to n state depends on the square of the amplitude
of the electric field , the time of irradiation t and the square of the transition dipole moment nm in
the definite integral form is
+

nm = () (x) dx.

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

(ii) Population of energy states: Intensity of a spectral line depends on the number of absorbing
species (molecules, atoms, nuclei) undergoing the transition from the lower to higher energy state.
This in turn depends on the population of the absorbing species in the lower energy state. The
population of an energy state relative to the lower one is given by the Boltzmann distribution as

Where , E is the difference between E upper and E lower, T is absolute temperature and k is
Boltzmann constant having value 1.38 X 10-23 JK-1.
(iii) Concentration and path length of the sample: If the concentration of the sample or its path
length is increased, intensity of absorption increases. More the concentration of the sample, more
intense is the spectral line.
The relationship between intensity (I0) before absorption, intensity (I) after absorption,
concentration of the sample (C) and path length (L) is given by Beer- Lambert`s law.
I / I0 =

Where k is a constant for a particular transition. I / I0 = = T

The above equation can be written as:


T is the Transmittance and is called the molar absorption coefficient. is called the molar
absorption coefficient. depends on the wavelength and nature of absorbing material. Its unit is mol 1
dm3cm-1. log (I / I0) = = Absorbance (A) or optical density.
Spectroscopic transitions:
When a system is exposed to external radiation, three processes may occurm (i) the system
may absorb radiation (induced absorption) (ii) the system may emit radiation (induced emission), and
(iii) the system may spontaneously emit radiation (spontaneous emission) to go from state n to state
m (n>m). If the transition probability for the three events are represented as Imn, Inm and Snm, then the
Number of induced absorptions per second = NmImn()
Number of induced emissions per second = NnInm()
Number of spontaneous emissions per second = Nm Snm
Here () is the density of incident radiation of frequency and Nm, Nn are the total number
of absorbers in m and n states respectively.
Of the three events, spontaneous emission occurs to the least extent compared to the other
two. So if it is ignored, the intensity of the absorption line will be dependent only on induced
absorption and emission. In general, the intensity of absorption line depends on the population in the
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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

lower state. Since the induced emission is coherent with the induced absorption, the net absorption
intensity is given by
Net absorption intensity = Number of induced absorptions per second
- Number of induced emissions per second
= NmImn() - NnImn() = Imn()[ Nm - Nn]
(Since Imn = Inm),
Thus the intensity of absorption depends on the difference in the population in states m and nm
assuming () to be constant.
Signal to noise ratio: Every recorded spectrum has a background of random fluctuations caused by
spurious electronic signals (unwanted radiations from source) produced by the source or detector, or
generated in the amplifying equipment. These fluctuations are usually referred as noise. In order
that a real spectral peak should show itself as such and be sufficiently distinguished from the niose, it
must have an intensity some three or four times that of the intensity of observable signals.
BORN-OPPENHEIMER APPROXIMATION:
The total wave function in a many electron system is separated into an electronic and a
nuclear part using Born-Oppenheimer approximation. According to this approximation, the nuclear
and electric motions are assumed to be independent of each other. Because of their vast difference in
mass, the nucleus may be considered to be stationary when the electrons move, so that the electronic
wave function can be obtained by the electronic part of the overall wave function for fixed position
of the nucleus.
For a many multielectronic system, the time independent Schrodinger wave equation is given
by
2

[ 2 2 2 2 + `

`
`

2- 2 + ` ] = E

Where, Mj = mass of the jth nucleus, mi = mass of the ith electron, 2 is laplacian operator
rij is the distance between the ith electron and the jth nucleus, rjj` is the distance between the nuclei i
and j`, rii` is the distance between the electrons i and i`, e is the unit electronic charge and E is total
energy of the system and Zi and Zj` are the atomic numbers of the nuclei.
The first two terms, represent the kinetic energies of the nuclei and the electrons
respectivgely. The rest represent either repulsion between the nuclei and the electrons respectively.
The rest represent either repulsion between the nuclei or between the electrons, or attraction between
the nuclei and electronic motion.

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2014

When Born-oppenheimer approximation is operative, the nuclear kinetic energy term is


excluded while considering the electronic motion. So equation becomes,
2

[ 2 2 + `

`
`

2- 2 + ` ]e = Ee

When the positions of the nuclei are considered to be fixed, the term `
so that the electronic energy is expressed as Ee = E - `
2

`
`

`
`

2 becomes constant

[ 2 2 - 2 + ` ]e = Eee

Consiquently, the nuclear wave function is given by


2

[ 2 2 + `

`
`

2 ]n = Enn

Thus the total wave function of a system can be separated into an electronic and a nuclear part using
this approximation. Solutions to equations 25 and 26 yield the corresponding energy values so that
the total energy E of the system can be expressed as
E = En + Ee
In other words, the nuclear (En) and electronic (Ee) energies act independently and these do not
interact with each other.
Born-Oppenheimer approximation may be extended further to separate the vibrational and
rotational motions in a molecule. Nuclear motions, apart from spin motion are contributed by the
translational, vibrational and rotational motions of the molecule. So use of Born-Oppenheimer
approximation permits one to separate the rotational, vibrational, translational and nuclear spin
functions, provided such motions are independed of one another.
=
and

En = Evib + Erot + Etrans + Ens

Since the translational energy and the energy due to nuclear spin are negligible, it follows
therefore, En = Evib + Erot
The above equation forms the basis for analyzing the vibrational- rotational spectra of
molecules. It is assumed that the vibration and rotation in molecules occur independent of each other
so that the net energy of transition may be taken as the sum of energy changes in individual event.
Although the approximations are successful to some extent in explaining the spectral properties of
molecules, it is limited to transitions involving lower J values. Deviation is observed for transitions
involving rotational energy levels with high J values (J is the rotational quantum number).
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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

ATOMIC SPECTROSCOPY (Electronic spectroscopy of atoms)


The electromagnetic spectrum, A general discussion on various molecular excitation processes,
Spectra of hydrogen and hydrogen like atoms, alkali metals spectra, L-S coupling, Term symbols,
Space quantisation, Zeeman effect, Stark effect, Paschen-Back effect.
Atomic quantum numbers
Quantum number
Principal, n
Orbital, l

Allowed values
1,2,3,..
(n-1), (n-2),.0

Magnetic, m

l, ( l 1),.0

Spin, s

+2

Function
Governs the energy and size of the orbital
Governs the shape of the orbital and the electronic
angular momentum
Governs the direction of an orbital and the electrons
behavior in a magnetic field
Governs the axial angular momentum of the electron

Energies of atomic orbitals:


The energies of each orbital vary considerably from atom to atom. There are two main
contributions of energy (i) Attraction between electrons and nucleus, (ii) Repulsion between
electrons in the same atom.
Hydrogen atom
This is the simplest because factor (ii) is absent. Because of the absence of interelectronic effects all
orbitals with the same n value have the same energy in hydrogen. Thus the 2s and 2p orbitals, for
instance, are degenerate, as are the 3s, 3p and 3d. However, the energies of the 2s, 3s,4s,.. orbitals
differ considerably. For the s orbitals given by

= ( )

)
0

Where0 =

2
4 2 2

and energy is = 83 2 2 =

cm-1 (n = 1,2,3..)

, r is the radial distance from the nucleus, ( ) is a power series of degree (n0

1) in , n is principal quantum number, which can have values 1,2,3, . The dimension of 0 is
0

the vacuum permittivity. R is the Rydberg constant. Since, p,d,. Orbital shave the same energies as
the corresponding s (for hydrogen only).
When an electric discharge is passed through gaseous hydrogen, the H2 molecule dissociate and the
energetically excited hydrogen atoms are produced. These emit electromagnetic radiation of discrete
frequencies. The hydrogen spectrum consists of several series of lines named after their discoverers.

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2014

Line spectrum of Hydrogen:


Series
Lyman
Balmer
Paschen
Brackeett
Pfund

n`
1
2
3
4
5

n``
2,3,..
3,4,..
4,5,..
5,6,..
6,7,.

n=
n=5
n=4

Spectral region
Ultraviolet
Visible
Infrared
Infrared
Infrared

n=3
n=2

Pfund
series
Balmer
series,
Red, Green,Blue,
Violet

Lyman series
1s

n=1

The lowest value of n = is plainly n = -Rcm-1 (where n = 1), and so this represents most stable (or
ground) state; n increases with increasing n, reaching a limit n = 0 and for n = . This represents
complete removal of the electron from the nucleus, i,e., the state of ionization. We sketch these
energy levels for n = 1 to 5 and l = 0, 1 and 2 only. The three p states and five d states for each n are
degenerate and not shown separately.
The electronic energy level and transition between them for the single electron of the hydrogen atom
depends upon the selection rules which are obtained from Schrdinger equation, i.e.,
Selection rules: = anything and = 1 only
Result:
An electron in the ground state (the 1s) can undergo a transition into any p state: 1s np (n 2).
A 2p electron can have transitions either into an s state or a d state: 2p ns or nd
Since s and d orbitals are here degenerate the energy of both these transitions will be identical. These
transitions are sketched.
In general, an electron in a lower state n can undergo a transition into a higher state n, with

absorption of energy; = n - n cm-1. spect. = `2 ( ``2 ) = R{``2

1
`2

} cm-1.

An identical spectral line will be produced in emission it the electron falls from n` to state n``. In
both cases l must change by unity. Let us consider transitions, restricting ourselves to absorption for
simplicity.

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

l=0
s state
n=
n=5
n=4

l=1
p state

l=2
d state

2014

Energy
cm-1
0

n=3

5s
4s
3s

3p

n=2

2s

2p

5p

5d
4d
3d

4p

3R/4

8R/9 15R/16
R
24R/25

-0.2R

80K 85K 90K 95K 100K 105K 110K cm-1

-R

1s

n=1

Representation of part of the Lyman series


of the hydrogen atom, showing the
convergence (ionization) point

Some of the lower electronic levels and transitions


between them for single electron of the hydrogen atom

Transitions 1s n`p, n` = 2,3,4..For these


1

lyman = R{12 `2} = R - `2 . Cm-1

3 8 15 24
4

16

25

.. cm-1(for n` = 2,3,4,5,.) R = 109 677.581cm-1.

Hence we expect a series of lines at the wave numbers given above. Just such a series is indeed
observed in the atomic hydrogen spectrum, and it is called the Lyman series after its discoverer. This
convergence limit, which arises when n` = , is shown dashed on the figure. It plainly represents
removal of the electron- i.e., ionization and the energy required to ionize the atom is given, in cm-1,
by the value of R. (1cm-1 = 1.987 x 10-23J).
Another set of transitions arises from an electron initially in the 2s and 2p states; 2s n`p or 2p
n`s, n`d. For these we write,
1

5 3 21

Balmer = R{4 `2 } cm-1 36 , 16 , 100 , .. cm-1(for n` =3,4,5,..)


Thus we expect another series of lines converging to
series, is observed and the value of

1
4

1
4

cm-1 (n` = ); this siries, called as Balmer

obtained from its convergence limit which represents the

ionization potential from the first excited state is in agreement with the value of R from the Lyman
series.
Other similar line series (called the Paschen, Brackett, Pfund, etc., series) are observed for n``
=3,4,5,.; All these spectral lines were correlated empirically by Rydberg, and he showed that an
equation which describes the wave numbers of each spectral lines.
Convergence limits: It should be mentioned that each line series discussed above shows a
continuous absorption or emission to high wave numbers of the convergence limits. The convergence
limit represents the situation when the atomic electron has absorbed just sufficient energy than this
and hence escape with higher veleocities and, since the kinetic energy of an electron moving in free
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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

space is not quantizedm any energy above the inonization energy can be absorbed. Hence the
spectrum in this region is continuous.
Fine structure of Hydrogen Spectrum:
Electronic angular momentum:
Orbital angular Momentum:
An electron moving in its orbital about a nuleus possesses orbital angular momentum, a measure of
which is given by l value corresponding to the orbital. This momentum is, ofcourse, quantized, and it
is usually expressed in terms of the unit h/2,

Orbital angular momentum (I) = ( + 1) . 2 units


Orbtital Angular momentum is a vector quantity; along with its direction its magnitude is also
important.
The Orbital angular momentum vector of an electron could not point in an infinite number of
different directions (i.e., quantized).
lz
lz

+2

sz

+1

+1/2

+1
0

l = 2

l = 6

s = (1/2)3

0
-1/2

-1

-1
-2

(a) l = 1

(b) l = 2

(c) s = 1/2

The allowed directions of the electronic angular momentum vector for an electron in (a) a p state (l
=1), (b) a d state (l =2), and (c) the allowed directions fo the electronic spin angular momentum
vector. The reference direction is taken arbitrarily as upwards in the plane of the paper.

The reference direction, here taken to be vertical in the figure, is conventionally used to define z axis,

and so we can write the components if I is this direction Iz, Alternatively, Iz = lz. 2. There are 2l+1
values of lz m for a given l. Plainly lz mis to be identified with magnetic quantum number m.( lz
m), m governs essentially direction of an orbital.
For lz m= l, l-1, l-2,..0..-(l-2), -(l-1), l (all are degenerate)

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2014

For l =0, lz m has 2(0)+1 = 1 value , for l =1, lz mhas 2(1)+1 = 3 values (+1, 0, -1), and for l =2,
lz m has 2(2)+1 = 5 values (+2, +1, 0, -1, -2).
l

l is the orbial quantum number (integer, positive or zero) representing the state of an electron in
an atom and determining its orbital angular momentum.

The vector l designates the magnitude and direction and is equal to ( + 1) . 2 units.

lz l is the orbial quantum number in the direction z axis


Iz The vector l designates the magnitude and direction along z- axis ( and is equal to lz h/2units)

Electron Spin Angular Momentum: Every electron in an atom can be considered to be spinning
about an axis as well as orbiting about the nucleus. Its spin motion is designated by the spin quantum
1

number s, which can be shown to have a value of 2 only. Thus the spin angular momentum is given
by

1 3

s = ( + 1) . 2 = 2 . 2 units = 2 3 units
The quantization law for spin momentum is that the vector can point so as to have components in the
reference direction which are half integral multiplies of h/2. i.e., so that sz = sz h/2 with sz taking
1

the values +2 2 only. The two (that is 2s+1) allowed directions and are degenerate.
Total Electronic angular momentum: j = l +s
Where j is the total angular momentum. Since l and s are vectors, hence j is also a vector.

j = ( + 1) . 2 = ( + 1) units
Where j is half-integral (since s is half-integral for a one-electron atom), and a quantum law applies
equally to j as to l and s : j ca have z-components which are half-integral only, i.e.,
1

jz = j, (j-1), (j-2),. 2.
There are two methods by which we can deduce the various allowed values of j for particular l and s
values.
1. Vector summation: In ordinary mechanics, two forces in different directions may be added by a
graphical method in which vector arrows are drawn to represent the magnitude and direction of the
forces, the parallelogram is completed, and the magnitude and direction of the resultant given by the
diagonal of the parallelogram. Exactly the same method can be used to find the resultant (j) of the
vectors l and s. The importance difference is that quantum mechanical laws restrict the angle

20

2014

VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

between l and s to values such that j is given by the equation with half-integral. Thus j can take
2

1 3 5

35, .. corresponding to j = 2 , 2 , 2,.

l = 1( that is l = 2) and s = 2 ( =
The summation yields j =
3

1
2

1
2

3 ).

15 which

1
5

corresponds to a j value of 2 i.e., 1+ 2.


1

l = 1( that is l = 2) and s = 2 ( =
The summation yields j =
3

1
2

1
2

/2
)

15,

l = 2

3 ).

(1

j=

values, 2 3,

l = 2

j= (1/2)3

15 which
1

s = (1/2)3

s = (1/2)3
(a)

corresponds to a j value of 2 i.e., 1+ 2.

(b)

The two energy states having different total angular


momentum which can arise as a result of the vector
addition l = 2 and s = (1/2)3

Summation of z components: If the components along a common direction of two vectors are
added, the summation yields the component yields the component in that direction of their resultant.
1

We have seen that the z-components of l = 1 are 1 and 0, while those of s = 2 are 2 only. Tking all
possible sums of these quantities, we have,
1

3 1 1

jz = lz + sz, jz = 1+ 2, 1- 2, 0+ 2, 0- 2, -1+ 2, -1- 2 = 2 , 2 , 2 , 2 , 2 , 2


3

In this list of six jz components, the maximum value is 2, which we know must belong to j = 2. Other
3

components of j = 2 are 2, - 2 and - 2 and, striking these from the above six, we are left with j = 2.
3

Thus all the six components are accounted for if we say that the states j = 2 and j = 2 may be formed
1

from l = 1 and s = 2. For a p electron (that is l =1), the orbital and spin momentum may be combined
1

to produce a total momentum of j = 2 15 when l and s reinforce (physically we would say that the
1

angular momenta have the same direction) ot to give j = 2 3 when l and s oppose each other. Thus
the total momentum is different in magnitude in the two cases and hence we have arrived at two
different energy states depending on whether l and s reinforce or oppose. Both energy states are p
states, however (since l is a for both) and they may be distinguished by writing the j quantum number
value as a subscript to the state symbol P, thus: P3/2 or P1/2. (We, here, use a capital letter for the state
of a whole atom and a small letter for the state of an individual electron; in the hydrogen atom, which
contains only one electron) States such as these, split into two energies, are termed doublet states;
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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

their doublet nature is usually indicated by writing a superscript 2 to the state symbol, thus; 2P3/2,
2
P1/2. The state (or atom) symbols produced are to be read doublet P three halves or doublet P one
half, respectively.
All other higher l values for the electron will obviously produce doublet states when combined with s
1

= 2; for instance, l = 2, 3, 4, will yield 2D5/2, 2D3/2 (or it can be written as 2D5/2, 3/2), 2F7/2,5/2, 2G9/2,7/2
etc. For l = 0, it can make no contribution to the vector sum, and the only possible resultant is s =
1
2

3 or s = 2. Remember that s = - 2 is not allowed, since the quantum number cannot negative; it is

only the z component of the vector which can have negative values. Thus for an s electron we would
hve the symbol S1/2 only. This is nonetheless formally written as a doublet state (2S1/2).
Fine structure of the hydrogen atom:
Energy (cm-1)
2

S1/2
j

4s
3s

1/2
1/2

2p
3p

P1/2,3/2
j
3/2
1/2
3/2
1/2

D3/2,5/2
j

4d
3d

5/2
3/2
5/2

-2.0 R

3/2

3/2
2s
1/2

2p
1/2

-1.0 R

1s
1/2

Some of the lower energy levels of the


hydrogen atom showing the inclusionof
j-splitting. The splitting is greatly
exaggerated for clarity

The hydrogen atom contains one electron and so the


coupling of orbital and spin momenta and consequent
splitting of energy levels will be exactly as described
above. Each level is labeled with its n quantum
number on the extreme left and its j value on the right;
the l value is indicated by the state symbols S, P, D,
at the top of each column. The separation between
levels differing only in j is many thousands of times
smaller that the separation between levels of different
n. However, the j-splitting decreases with increasing n
and with increasing l. The F, G, states, not shown
on the diagram, follow the same pattern.
The selection rules for n and l are the same as before:
n = anything, l = 1 only, but now there is a
selection rule for j; j = 0, 1.
These selection rules indicate that transitions are
allowed between any S and any P level;
2
S1/2 2P1/2 (j = 0)
2
S1/2 2P3/2 (j = +1)

Thus the spectrum to expect from the ground (1s) state will be identical with the Lyman series except
that every line will be a doublet, In fact, the separation between the lines is too small to be readily
resolved, but we shall shortly consider the spectrum of Sodium in which this splitting is easily
observed.

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

D5/2

D3/2

P3/2

P1/2

cm-1
The 'compound doublet'
spectrum arising as the
result of transitions
between 2P and 2D
levels in the hydrogen
atom

2014

Transition between the 2P and 2D states are rather more complex;


Following Figure shows four of the energy levels involved.
Plainly the transition at lowest frequency will be that between the
closest pair of levels, the 2P3/2 and 2D3/2. This, corresponding to j
= 0, is allowed. The next transition, 2P3/2 2D5/2 (j = +1), is also
allowed and will occur close to the first because the separation
between the doublet D states is very small. Thirdly, and more
widely spaced, will be 2P1/2 2D3/2 (j = +1), but the fourth
transition (shown dotted), 2P1/2 2D5/2, is not allowed since for
this j = +2.
Thus the spectrum will consist of the three lines shown at the foot
of the figure. This, arising from transitions between doublet
levels, is usually referred to as a compound doublet spectrum.
The inclusion of coupling between orbital between orbital and
spin momenta has led to a slight increase in the complexity of the
hydrogen spectrum. In practice, the complexity will be observed
only in the spectra of heavier atoms, since for them the j-splitting
is larger than for hydrogen. In practice, however, all the lines in
the hydrogen spectrum should be close doublets if the transitions
involve s levels, or compound doublets if s electrons are not
involved.

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2014

MANY-ELECTRON ATOMS:
SPECTRUM OF LITHIUM AND OTHER HYDROGEN-LIKE SPECIES:
The energy levels of lithium are Sketched in the figure, which should be compared with the
corresponding Hydrogen. The two diagrams are similar except for the energy difference between the
s, p and d orbitals of given n in the case of lithium and the fact that, for this metal, the 1s state is
filled with electrons which do not generally take part in spectroscopic transitions, as it requires much
less energy to induce the 2s electron to undergo a transition.
The selection rules for alkali metals are the same as for hydrogen, that is n = anything, l =
1, j = 0, 1 and so the spectra will be similar also. Thus transitions from the ground state (1s22s)
can occur to p levels: 2S1/2 n 2P1/2,3/2, and a series of doublets similar to the lyman series will be
formed, converging to some point from which the ionization potential can be found.
From the 2p state, however, two separate series of lines will be seen:
2 2P1/2,3/2 n 2S1/2 and 2 2P1/2,3/2 n 2D3/2,5/2

The former will be doublets, the latter compound doublets, but their frequencies will differ
because the s and d orbital energies are no longer same.
The same remarks apply to the other alkali metals, the difference between their spectra and
that of lithium being a matter of scale only. For instance, the j-splitting duw to coupling between l
and s increases markedly with the atomic number. Thus the doublet separation of lines in the spectral
series, which is scarcely observable for hydrogen, is less than 1cm-1 for the 2p level of lithium, about
17cm-1 for sodium, and over 5000cm-1 for cesium.
Any atom which has a single electron moving outside a closed shell will exhibit a spectrum
of the type discussed above. Thus ions of the type He+, Be+, B2+, etc should, and indeed do, show
what are termed as hydrogen-like spectra.
ANGULAR MOMENTUM OF MANY ELECTRON ATOMS:
When two or more electrons in the outer shell then the total angular momentum of the atom
may be obtained in two ways.
1. Russell-Saunders coupling (R-S coupling, applicable to small to medium sized atoms):
First sum the orbital contributions, then the spin contributions separately, and finally add the total
orbital and total spin contributions to reach the grand total.
= L

= S

L+S=J
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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

Where use bold-face capital letters to designate the momentum


2. j-j coupling (individual j`s are summed, applicable to larger atoms):
Sum the orbital and spin momenta of each electron separately, finally summing the individual totals
to form the grand total;
+ = ji

and

= J

Summation of Orbital angular momentum:


L = l1 + l2, l1 + l2 - 1, l1 + l2 - 2, l1 + l2 3, l1 - l2 for two electrons there will be 2l+1
different values of L, where li is the smaller of the two l values.
This is applicable to individual electrons concerned different n or different l values ( these are termed
as non-equivalent electrons)
Summation of Spin contributions:
Summation of individual quantum numbers
S = , -1, -2, ..

= 2,

= 2,

1, .2 (for N odd)
1

1, .2 (for N even)
2

Total angular momentum:


J = L + S, L + S -1, L + S -2,. L - S
3

7 5 3

For example, if L = 2, S = 2, we would have J = 2 , 2 , 2

1
2

While if L = 2, S = 1, the J values are J = 3, 2 or 1 only


Term symbol:
Term symbol = Spin multiplicity Total orbital angular momentum Total angular momentum = 2S +1 L J

SPECTRUM OF HELIUM AND THE ALKALINE EARTHS:


Helium atomic number two, consists of a central nucleus and two outer electrons. Clearly
there are only two possibilities for the relative spins of the two electrons:

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2014

1. Their spins are paired: in which case if s1z is +1/2, s2z must be -1/2; hence S = s1z + s2z = 0, and so
S = 0 and we have singlet states.
2. Their spins are parallel: now s1z = s2z = +1/2, say, so that Sz = 1 and the states are triplet.
The lowest possible energy state of this atom is when both electrons occupy the 1s orbital;
this by Pauli`s principle, is possible only if their spins are paired, so the ground state of helium must
be a singlet state. Further L = l1 +l2 = 0. And hence J can only be zero. The ground state of helium,
therefore, is 1S0.
The relevant selection rules for many-electron systems are: S = 0, L = 1 and J = 0, 1
Since S cannot change during a transition, the singlet ground state can undergo transitions only to
other singlet states. The selection rules for L and J are the same as those for l and j condidered
earlier.
For the moment we shall imagine that only one electron undergoes transitions, leaving the
other in the 1s orbital, and the left hand side of figure shows the energy levels for the various singlet
states which arise.
Initially the 1s2 1S0 state can undergo a transition only to 1s1np1 states (abbreviated to 1snp);
in the latter L = 1, and S = 0, and hence J = 1 only, so the transition may be symbolized;
1s2 1S0 1snp 1P1 or 1S0 1P1
From the 1P1 state the system could either revert to 1S0 states, or undergo transitions to the
higher 1D2 states (for these S = 0, L = 2, and hence J = 2 only). In general, then, all these transition
will give rise to spectral series very similar to those of lithium except that here transitions are
between singlet states only and all the spectral lines will be single.
Returning to the situation in which the electrons spins are parallel (case 2, the triplet states)
we see that, since the electrons are now forbidden by pauli`s principle from occupying the same
orbital, the lowest energy state is 1s2s. This and other triplet energy levels are shown on the right
side. The 1s2s state has S = 1, L = 0 and hence J = 1 only (i.e., modulus L+ S to L-S) and so it is 3S1;
by the selection rules it can undergo transitions into the 1snp triplet states, these with S = 1, L = 1,
have J = 2, 1, 0 (i.e., modulus L+ S to L-S) and so the transitions may be written.
3

S1 3P2, 3P1, 3P0

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

3
3

D3

D2

D1

3
3

P2

P1

P0
Cm-1

The 'compound triplet spectrum


arising from transitions between
3
P and 3D levels in the helium.
The separation between levels
of different j is much
exaggerated.

2014

All Three transitions are allowed, since J = 0 or 1, so the


resulting spectral lines will be triplets.
Transitions from the 3P states may take place either to 3S
states (spectral series of triplets) or to 3D states. In the latter
case, the spectral series may be very complex of completely
resolved. For 3D we have S = 1, L =2, and hence J = 3, 2 or 1,
and hence a transition between 3P and 3D states, bearing in
mind the selection rule J = 0 or 1. Note that 3P2 can go to
each of 3D3,2,1, 3P1 can go only to 3D2,1, and 3P0 can go only to
3
D1. Thus the complete spectrum should consist of six lines.
Normally, however the very close spacing is not resolved, and
only three lines are seen; for this reason the spectrum is referred
to as a compound triplet.
The spectrum of helium consists of spectral series
grouped into two types which overlap each other in frequency.
In one type, involving transitions between singlet levels, all the
spectral lines are themselves singlets, while in the other the
transitions are between triplet states and each line is at least a
close triplet and possibly even more complex.
Because of the selection rule S = 0, there is strong
prohibition on transitions between singlet and triplet states, and
transitions cannot occur between right and lecft hand sides of
figure.

Other atoms containing two outer electrons exhibit spectra similar to that of helium. Thus the
alkaline earths, beryllium, magnesium, calcium, etc., fall into this category, as do ionized species
with just two remaining electrons, for example, B+, C2+, etc.
Note at this point that the above discussion on helium has been carried through on the
assumption that one electron remains in the 1s orbital all the time. This is a reasonable assumption
since a great deal of energy would be required to excite two electrons simultaneously, and this would
not happen under normal spectroscopic conditions. However, not all atoms have only s electrons in
their ground state configuration.

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2014

ZEEMAN EFFECT:
Principle: Angular momentum can be considered as arising from a physical movement of electrons
about the nucleus and, since electrons are charged such motion constitutes a circulating electric
current and hence a magnetic field. This field can, indeed, be detected and it is its interaction with
exterior fields which is the subject of this effect.
Representation of magnetic field: This can be represented using angular momentum field by a
vector - the magnetic dipole of the atom, and is readily that is directly proportional to theangular
momentum J and has the same direction.
Representation in terms of Classical mechanics:
If the electron is considered as a point mass m and charge e, then =
1T = 10,000 gauss in electromagnetic unit)

JT-1

(SI unit,

Representation in terms of Quantum mechanics:


However, Quantum mechanics indicates that the electron is not a point charge and a more exact
g

expression for is, = ( + )


JT-1
Where g is a purely numerical factor, called the Lande splitting factor. This factor depends on the
state of the electrons in the atom and is given by
g=1+

(+1)+ (+1) (+1)


2(+1)

(+1) (+1)
2(+1)

In general, g lies between 0 and 2.

Recapitulate:
Orbital, l

(n-1), (n-2),.0

Magnetic,
ml

l, ( l 1),.0

Governs the shape of the orbital and the electronic angular


momentum
Governs the direction of an orbital and the electrons behavior in
a magnetic field, and has 2(l +1) components, ml = l, l-1,0,-l
lz

lz

+2

sz

+1

+1/2

+1
0

l = 2

l = 6

s = (1/2)3

0
-1/2

-1

-1
-2

(a) l = 1

(b) l = 2

(c) s = 1/2

The allowed directions of the electronic angular momentum vector for an electron in (a) a p state (l
=1), (b) a d state (l =2), and (c) the allowed directions fo the electronic spin angular momentum
vector. The reference direction is taken arbitrarily as upwards in the plane of the paper.

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

J can have either integral or half-integral components Jz along a reference direction, depending upon
whether the quantum number J is integral or half-integral.
For example consider one electron system and that to it is in p orbital, then, For a state J = 3/2, the
2J +1 components being given by Jz = J, J-1,1/2 or 0,-J
Further, since is proportional to J, will also have components in the z direction which are given
g
by z =
If now external field is applied to the atom, thus specifying the previously arbitrary z direction, the
atomic dipole mu will interact with applied field to an extent depending on its component in the field
direction. If the strength of the applied field is Bz then the extent of the interaction is simply z Bz:
Interction = E = z Bz = (
Jz
+3/2
+1/2

) Bz =

+3/2

Bz J

Applied field Bz

+1/2
-1/2
-3/2

No field

E
E

-1/2
-3/2
(a) z components of J

Jz
+3/2
+1/2
-1/2

-3/2
(b) z components of the (c) Splitting of energy
magnetic dipole
levels with different J

The effect of an applied magnetic fiels on the enrgy leves of an electron with
J = 3/2, In (a) the 2J = 4 components of J are shown, in (b) their
corresponding magnetic moments in the reference direction and in (c) an
external field splits the originally degenarate levels into four separate levels

In this equation, the


interaction can be expressed
as E since the application
of the field splits the
originally
degenerate
energy levels corresponding
to the 2J+1 values of Jz into
2J+1
different
energy
levels. This is shown for J
= 3/2 in fig(c). It is this
splitting, or lifting of the
degeneracy
on
the
application of an external
magnetic field, which is
called the Zeeman effect.

Definition: The splitting of spectral lines in the presence of an applied field B (called the magnetic
flux density) is called the Zeeman Effect, first observed by P. Zeeman in 1896.
The energy splitting is very small; the factor he/4m is known as Bohr magneton, hass a value of
9.27 X10-24 JT-1; thus for g = 1, and ofr an applied field Bz of one tesla (that is 10000gauss) the
interaction energy is only some 10-23 joules, which is in turn is of the order of 0.5 cm-1. This small
splitting is, of course, reflected in a splitting of the spectral transitions observed when a magnetic
field is applied to an atom. In order to discuss the effect on the spectrum, we need one further
selection rule. Jz = 0, 1
Let us consider the doublet lines in the sodium spectrum produced, as we have discussed in earlier
section, transition between the 2S1/2 2P1/2 (j = 0), 2S1/2 2P3/2 (j = +1) states.
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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

When a field Bz is applied to the atom, the atom, the 2S1/2 and 2P1/2 states are both split into two
(since J = , 2J +1 = 2), while the 2P3/2 is split into four. The extent of the splitting is proportional to
the g factor in each state and, from, we can easily calculate:
2

S1/2: S = , L = 0, J = , hence g = 2

P1/2: S = , L = 1, J = , hence g = 2/3

P3/2: S = , L = 0, J = , hence g = 4/3

And we that, 2S1/2, 2P1/2 and 2P3/2 levels are split in the ratio 3: 1: 2.
Field applied

Energy (cm-1)
2

S1/2
j

4s
3s

1/2
1/2

2p
3p

P1/2,3/2
j
3/2
1/2
3/2
1/2

j
4d
3d

No field

D3/2,5/2
0

1/2

P3/2

-2.0 R
3/2

3/2
2s

5/2
3/2
5/2

Jz
+3/2
+1/2
-1/2
-3/2

2p

+1/2
-1/2

P1/2

1/2

-1.0 R

1s

+1/2

1/2

Some of the lower


energy levels of the
hydrogen
atom
showing
the
inclusionof j-splitting.
The
splitting
is
greatly exaggerated
for clarity

S1/2
Cm-1

-1/2

The zeeman effect on transitions between 2S and 2P states. the situation


before the field is appliedis shown on the left, that after on the right

On the left of the figure we see that the energy levels and transitions before the field Bz is applied;
the levels are unsplit and the spectrum is a simple doublet. On the right, we see the effect of the
applied field. The spectrum shows that the original line due to the 2S1/2 2P1/2 transition disappears
and is replaced by four new lines, while the 2S1/2 2P3/2 transitions is replaced by six new lines.

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

The effect described above is usually referred to as the anomalous Zeeman Effect-although, infact,
most atoms show the effect in this form. The normal Zeeman effect applies to transitions between
singlet states only (e.g., the transitions of electrons in the helium atom shown on left side)
For singlet states we have 2S +1 = 1 hence S = 0 Therefore, J = L and g = 1
Thus the splitting between all singlet levels is identical for a given applied field and the
corresponding Zeeman spectrum is considerably simplified.
In general, the Zeeman Effect can give very useful information about the electronic states of atom. In
the first place, the number of lines into which each transition becomes split when a field is applied
depends on the J value of the states between which transitions arise.
Next the g value, deduced from the splitting for known applied field gives information about L and S
values of the electron undergoing transitions. Overall, then the term symbols for various atomic
states can be deduced by Zeeman experiments. In this way, all the details of atomic states, term
symbols, etc discussed above, have been conformed experimentally.

Classic theory of the Raman effect: Molecular polarizibility


When a molecule is put into a static electric field it suffers some distortion, the positively charged
nuclei being attracted towards the negative pole of the field, the electrons to the positive pole.
This separation of charge centers causes an induced dipole moment to be set up in the molecule and
the molecule is said to be polarized.
The size of the induced dipole , depends both on the magnitude of the applied field, E, and on the
ease with which the molecule can be distorted.
= E, where is the polarizibilty of the molecule.

H
H

Consider the diatomic molecule H2 in an electric field in fig (a) and (b) in end-on and sideways
orientation, respectively. The electrons forming the bond are more easily displaced by the field along
the bond axis (b) than that across the bond, and the polarizability is thus said to be anisotropic.
This fact may be conformed experimentally ( by a study of the intensity of lines in the Raman
spectrum of H2), when it is found that the induced dipole moment for a given field applied along the

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

axis is approximately twice as large as that induced by the same field applied across the axis; fields
in other directions induce intermediate dipole moments.
Polarisability ellipsoid: A three dimentional surface whose distances from the electrical center of the
molecule ( in H2 this is also the center of gravity)is proportional to 1/ where is the
polarizability along the line joining a point i on the ellipsoid with the electrical center. Thus where
the polarizability is greatest, the axis of the ellipsoid is least, and vice versa.
Imagine applying an electric field across the bond axis of H2, as figure (a) , a certain amount of
polarization of the molecule will occur. If we also imagine the molecule rotating about its bond axis,
it is obvious that it will present exactly the same aspect to the electric field at all orientations- i.e., its
polarizability will be exactly the same in any directionacross the axis. This means that a section
through the polarizability ellipsoid will be circular, which can be seen in figure (c)
If the field is applied along the bond axis , (b) the polarizability is greater as we meantioned earlied.
Thus the cross section of the ellipsoid is less, (d).
Polarizability ellipsoid is the inverse of an electron cloud-where the electron cloud is largest the
electrons are further from the nucleus and so are most easily polarized. This is represented by a
small axis for the polarizability ellipsoid.
All diatomic molecules have ellipsoids of the same general tangerine shape as H2, as do linear
polyatomic molecules, such as CO2, HCCH, etc. They differ only in the relative sizes of their major
and minor axes.
When a sample of such molecules is subjected to a beam of radiation of frequency v the electric
field experienced by each molecule varies according to the equation
E = E0 Sin 2t
And thus induced dipole also undergoes oscillations of frequency v;
= E = E0 Sin 2t
Such an oscillating dipole emits radiation of its own oscillation frequency and we have immediately
in the classical explanation of Rayleigh scattering.
If in addition, the molecule undergoes some internal motion, such as vibration or rotation, which
changes the polarizabililty, then the oscillating dipole will have superimposed upon it the vibrational
or rotational oscillation.
Consider, for example, a vibration of frequency vib which changes the polarizability,
= 0 + Sin 2 vib t

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

where 0 is the equilibrium polarizability and represents the rate of change of polarizability with
vibration.
= E = (0 + Sin 2 vib t) E0 Sin 2t
Using trigonometric relation:
1

SinA SinB = 2 { ( ) ( + )}
We have, = 0E0 Sin 2t +

1
2

0 { 2( ) 2( + )} and thus the

oscillating dipole has frequency components as well as the exciting frequency


1. If the vibration does not alter the polarizability of the molecule then = 0 and the dipole oscillates
only at the frequency of the incident radiation; the same is true for a rotation.
General rule: In order to be Raman active a molecular rotation or vibration must cause some change
in a component of the molecular polarizability is, of course, reflected by a change in either the
magnitude or the direction of the polarizability ellipsoid.
(This rule should be contrasted with that for infra-red and microwave activity, which is that the
molecular motion must produce a change in the electric dipole of the molecule.)
O

O
H

Cl

H
C
Cl

C
Cl

Cl

Cl

Cl

In particular case of H2O, the polarizability is found to be different along all three of the major axes
of the molecule (which lie along the line in the molecular plane bisecting the HOH angle, at right
angles to this in the plane, and perpendicular to the plane), and so all three of the ellipsoid axes are
also different; the ellipsoid is sketched in various orientations in figure. Other such molecules, for
example H2S or SO2, have similarly shaped ellipsoids but with different dimensions.
Symmetric top molecules, because of their axial symmetry, have polarizibility ellipsoids rather
similar to those of linear molecules, ie., with a circular cross section at right angles to their axis of
symmetry.

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

Finally, spherical top molecules, such as CH4, CCl4, SiH4, SF6 etc., have spherical polarizability
surfaces, since they are completely isotropic as far as incident radiation is concerned.
Pure Rotational Raman Spectra:
The rotational energy levels of linear molecules have already been stated
J = BJ(J+1) D J2 (J+1)2
cm-1 ( J = 0, 1, 2.,,,) but in Raman spectroscopy, the precision
of the measurement does not normally warrant the retention of the term involving D, the centrifugal
distortion constant. Thus we take the simpler expression; to represent the energy levels.
J = BJ(J+1) cm-1 ( J = 0, 1, 2.,,,)
Transitions between these levels follow the formal selection rule J = 0, 2 only
The fact that in Raman the rotational quantum number changes by two units rather than one is
connected with the symmetry of the polarizability ellipsoid. For a linear molecule, such such as
depicted, it is evident that during end-over-end rotation, the ellipsoid presents the same appearance to
an observer twice in every complete rotation.
It is equally clear that rotation about the bond axis produces no change in polarizability as in infrared and microwave spectroscopy.
The transition J = 0 is trivial since this represents no change in the molecular energy and hence
Rayleigh scattering only. Combinig, then, J = +2 the with the energy levels,
= J+2 - J = B(4J + 6) cm-1, since J = +2 may label these S branch lines and S = B(4J + 6)
Thus if the molecule gains rotational energy from the photon during collision we have a series of S
branch lines to the low wave number side of the exciting line (Stokes lines), while if the molecule
loses energy to the photon the S branch lines appear on the high wavenumber side (anti stokes lines).
The wave numbers of the corresponding spectral lines are given by
s = ex S = ex B(4J + 6) cm-1
where the plus sign refers to anti-stokes lines, the minus to stoke`s lines, and ex is the wave number
of the exciting radiation.
The allowed transitions and the Raman spectrum arising are shown schematically in fig. Each
transition is labeled according to its lower J value and the relative intensities of the lines are
indicated assuming that the population of the various energy levels varies according to eq and eq, In
particular it should be notated here that stokes and antistokes lines have comparable intensity
because many rotational levels are populated and hence down ward transitions are approximately as
likely as upward ones.

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

When the value J = 0 is inserted into equation, then the separation of the first line from the exciting
line is 6B cm-1, while the separation between successive lines is 4B cm-1.
For diatomic and light triatomic molecules, the rotational Raman spectrum will normally be resolved
and B value can be obtained, and hence the moment of inertia and bond lengths for such molecules.
Homonuclear diatomic molecules ( for example O2, H2) give no infra-red or microwave spectra since
they possess no dipole moment, whereas they do give a rotational Raman spectrum,
The Raman technique yields structural data unobtainable from the techniques previously discussed.
It is thus complementary to microwave and infra-red studies, not merely confirmatory.
If the molecule has a centre of symmetry (as, for example do H2, O2, CO2), then the effects of
nuclear spin will be observed in the Raman as in the infer-red. Thus for O2 and CO2 ( since the spin
of oxygen is zero) every alternate rotational level is absent; for example, in the case of O 2, every
level with even J values is missing, and thus every transition labeled J = 0, 2, 4, in fig is also
completely missing from the spectrum. In the case of H2 and other molecules composed of nuclei
with non-zero spin, the spectral lines show an alternation of intensity.
Linear molecules with more than three heavy atoms have large moments of inertia and their
rotational fine structure is often unresolved in the Raman spectrum. But in conjunction with the
infra-red spectrum, the Raman can still yield much very useful information.

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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

J=7

4
3
2
1
0

4B

4B
4B

4B
6B

8 7 6 5 4 3 2 1 0
Stokes lines

Cm-1

6B

0 1 2 3 4 5 6 7 8
Antistokes lines

Figure:The rotational energy levels of a diatomic molecule and the rotational Raman spectrum
arising from transitions between them. Spectral lines are numbered according to their lower J values.
Symmetric top molecules:
The polarizability ellipsoid for a typical symmetric top molecule, for example CHCl 3, was shown in
fig. Plainly rotation about the top axis produces no change in the polarizability, but end-over-end
rotations will produce such a change.
The energy levels
J, K = BJ(J+1) + (A-B)K2 cm-1 (J = 0,1,2.,,,,; K = 0, 1, 2,(J-1), J)
The selection rules for Raman spectra are:
K = 0
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VSSUT, , CHEM.DEPT., M.Sc, MCH-107,SPECTROSOCPY II, dr.ramakrishnavssut@gmail.com

2014

J = 0 (Rayleigh),
1 (R branch, positive sign for anti stokes lines and negative sign for stokes lines),
2 (S branch, positive sign for anti stokes lines and negative sign for stokes lines).
K = 0 implies that changes in the angular momentum about the top axis will not give rise to a
Raman spectrum such rotations, are, as mentioned previously, Raman inactive.
1. J = +1 (R branch lines)
R = J+1 - J = 2B(J+1) cm-1 (J = 1, 2, 3, (but J is not equal to zero))
2. J = +2 (S branch lines)
S = J+2 - J = 2B(2J+3) cm-1 (J = 0, 1, 2, 3,)
The two series of lines in the Raman spectrum:
R = ex R = ex 2B(J+1) cm-1
S = ex S = ex 2B(2J+3) cm-1
These series sketched separately in figure a and b, where each line is labeled with its corresponding
lower J Value. In the R branch, lines appear at 4B, 6B, 8B, 10B,cm-1 from the exciting line, while
the S branch series occurs at 6B, 10B, 14B,. cm-1. The complete spectrum, shown, illustrates how
every alternate R line is overlapped by an S line. Thus a marked intensity to be expected which, it
should be noted, is not connected with the nuclear spin statistics.
Spherical top molecules: (CH4, SiH4, SF6)
The polarizability ellipsoid for such molecules is a spherical surface and it is evident that rotation of
this ellipsoid will produce no change in polarizability. Therefore the pure rotations of spherical top
molecules are completely inactive in the Raman.
Asymmetric top molecules: (H2O)
All rotations of asymmetric top molecules, on the other hand are Raman active. Their Raman spectra
are thus quite complicated.

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