Molecular Spectroscopy

Course Code: CH 3240

Lect 1: General Introduction

Prof. Tarek A. Fayed

1. Course objectives and outline
2. Light and spectroscopy
3. Theoretical basics of spectroscopic techniques.
3.1. Microwave Spect.
3.2. IR and Raman Spect.
3.3. Electronic absorption Spect.
4. Applications of these techniques.
Course: Lecture 1 hours / week
Practical session 0 hours / week
Marks: 100

Assessment Method Proportion Marks

Written final examination 50% 50
Practical exam - -
Applied exam 15% 15
Semester work 20% 20
Oral assessment 15% 15
Spectroscopy and Electromagnetic Radiations

Spectroscopy is the technique that involves

study of the interactions between electro-
magnetic radiations (light) and matter (what-
ever atoms or molecules) and explanation of
the obtained spectral pattern (spectrum).
Spectrum is the output which shows how the
magnitude of the interactions between
electro-magnetic radiations and the matter
varies with the frequency (or Energy) of the
electromagnetic radiations.
 Aims of spectroscopy
Molecular spectra can be used to make:
1- Qualitative analysis of a new substance or a
mixture (to identify the molecular species).
2. Quantitative determination of a known
substance (using Beer-Lambert law).
3. Structural characterization of a substance (from
the energy levels and various transitions, the
physical and chemical properties of the
substance can be established). This is done by
using; IR, UV-Vis, NMR, Mass ESR and x-rays
techniques.
Fields of Applications of Spectroscopy
It is applied in the
shown fields;

To study the following;

Nature of electromagnetic radiations, EMR
It is a kind of electromagnetic energy that is
characterized by dual nature (Particles and Waves).
As waves; EMR can be characterized by wavelength (),
frequency (), velocity and amplitude. Electromagnetic
radiation requires no supporting medium for its
transmission and passes readily through a vacuum.

EMR

Properties of EMR
 Wave parameters

 Amplitude (A): Length of the electric vector at a

maximum in the wave.
 Period (P): The time (in seconds) required for the
passage successive maxima or minima through a fixed
point in space.
 Frequency (): The number of oscillations that occur
per second and is equal to 1/P. (; in s-1 or Hz).
 Wavelength (): The linear distance between any
two equivalent points on successive waves
(successive maxima or minima). ( ; in A, nm, etc.).
The particle Nature of Light: Photons
In many radiation-matter interactions, it is useful to
consider EMR as stream of discrete particles or wave-
packets of energy called photons.
The energy of the photon can be related to its
wavelength, frequency, and wavenumber by;

E = h = hc/ = hc
where, h is Planck’s constant (6.63 x 10-34 J s). The
wavenumber  and frequency , in contrast to the
wavelength , are directly proportional to the photon
energy E. The radiant power of a beam of radiation is
directly proportional to the number of photons per
second. c = velocity of radiation = 2.998108 m s-1 through
a vacuum
Theoretically,  (in cm-1) = 107 /  (nm)
 Interference of Spectral waves

Constructive Interference
1) Two waves have identical
frequency and in phase
2) f2 – f1 = d =  m2p
f2 – f1 = 0, or 360 deg or
integer of multiple of 360 deg.

Destructive Interference
1) Two waves have identical
frequency but out of phase
2) f2 – f1 = d = (2m+1)p
f2 – f1 = 180 deg or integer of
multiple of 360 deg.
When a substance absorbs
light, it goes from a lower
energy state (ground state)
to a higher energy state
(excited state).

 Only photons with energies

Only photons exactly equal to the energy
with energies exactly
equal to the
difference between energy
the twodifference
electronic states will be absorbed.
between the two electron states will
 Since different substances have different electronic shells which
be absorbed
are filled, they will each absorb their own particular type of light.
 The electromagnetic Spectrum
The interactions of radiations with chemical systems follow
different mechanism and provide different kinds of information.
So, many analytical methods (techniques) are based on the
interaction of radiant energy with matter.

Frequency (Hz)
Atomic or Molecular rotations
Valence
molecular electrons Molecular MW Nuclear Magnetic
transitions: Transitions vibrations resonance NMR
IR Electron Magnetic
UV-Vis resonance ESR
All electromagnetic radiation travels at the same speed, c
 Spectral  (nm)  (Hz) (cm-1) Energy Spectroscopic
range (kJ/mol) Technique
Radio ~1 x 109 ~108 ~0.03
~ ~10-8 NMR/ESR


Microwave ~100,000 ~1012 ~30 ~10-2 Rotational

Infrared ~1000 ~1014 ~3,000 ~103 Vibrational

Visible 400-750 4-6 x 1014 14,000- 1 – 3x105 Electronic

25,000 Absorption
Ultraviolet 100-400 ~1015 ~40,000 ~5x105 Electronic
Absorption
X ray <100 >1016 >100,000 >106 X ray
 Molecular Energy Levels and interactions between
light and matter
Radiations can be absorbed or emitted if the molecule changes
any of its energy levels (be excited or relaxed, respectivly)

Excited
Electronic
State

Vibrational
Rotational
Energy Levels
Energy Levels

Quantum v Ground
numbers Electronic
J State
n
Rotational Vibrational Electronic
Transition Transition Transition
 Interactions with Matter
Radio-wave; Changes nuclear and electron spin.
Microwave; Changes molecular rotations.
Infrared; Changes molecular vibrations.
Visible and Causes transition of outer shell
Ultraviolet; electrons from HOMO to LUMO.
Causes molecular dissociation
X-ray; Causes transition of inner shell
electrons.
-ray; Causes nuclear transitions.
 Basic components of Spectrometer
How the spectra can be measured?

Spectrometer is used
Spectra recorded by the Spectrometer
White-light covering a wide range of frequencies is
passed through a sample cell and then to a
monochromator (a prism or grating). Detector
(photodiode array) records the intensity of
transmitted light as a function of frequency or
records the absorbance as a function of wavelength
or wavenumber.
Frequency (υ)
A

T%

λ = Wavelength.
 Intensity
Intensity

 
Frequency Frequency
 Spectral features
1. Bands Position: It is determined by the wavelengths or the
frequencies at which the molecule absorb, it depends on its
structural features (Functional groups), as well as its environment
(solvent used). It is determined by the spacing between the
energy levels (i.e energy difference between energy levels
involved in the transition) not by the energy of the levels
themselves.
2. Width of spectral line: broadening of band is caused by;
• Collisional broadening (due to molecular-molecular interactions).
• Doppler broadening (molecular interactions in case of gases).
• Lifetime broadening (δE. δt  h/2π)
3. Intensity of spectral lines: It tells us about the;
• Transition probability (transition is allowed or forbidden).
• Population of states (how many molecule may interact).
• Path-length of the sample or conc. (-log (I/Io) = A = ε l c )
 1. Bands Position (Remember Energy Quantization)

E2
 E  E2  E1
ΔE
hc
 h   hc E1


A ε

wavelength wavelength
Band position Band position
 2. Width of spectral lines: (half- and base band width)

A A

A/2 A/2

Band width wavelength Band width wavelength

Spectral band broadening is due to:
i. Collision broadening

Inelastic collision:
Elastic collision:
The excitation energy
No energy from
is transferred from
internal degree of
the excited molecule
freedom is transferred
A* to a collision
during the collision.
partner B

• The collision of molecules causes the excited state to

revert to the ground state, shorten the lifetimes of the
excited state and leads to broadening of the associated
spectral lines.
 ii. Doppler broadening
 Occurs in the gaseous state, and increases with
temperature due to increasing differences between
the distribution of velocities of the molecules.
 The radiation frequency is shifted when the
absorbing or emitting molecule is moving towards
or away from the observer (light detector).
 Light source emits light photons with frequency  ,
the molecule is moving toward or away from the
stationary observer (detector) with velocity (±v),
then the observer measure the frequency not as
 but as - where;  v
   0 1 


 c
iii. Life-time broadening
 If a system exists in an energy state with energy
(E) for a limited time (τ = lifetime of this state).
The energy of that state will be uncertain to an
extent (δE).
According to Heisenberg Uncertainty Principle;

d E  d t  
h

2p
d t   uncerta int y in time  

1
Lifetime broadening in frequency 
2 pc 
Where  is the lifetime
example
 Calculate the lifetime broadening in
cm-1 for an excited state with lifetime
(τ = 1p.s.).
Note: 1p.s = 0-12 s.

1
Lifetime broadening in wavenumber 
2p c 
1
 12
2  3.14  2.998 10 110
10
The intensity of the spectral line
It is governed by;
1.Transition probability from which selection rules
can be obtained.
2. Population of the energy levels.
3. Path length of the sample.

Transition probability is governed by

transition moment M

Transition moment gives the probability of a transition between

two states (1) and (2) as a result of photon resonance
absorption obeying Bohr-Einstein conditions:
E2  E1  h c
The maximum value of molar
absorption coefficient
(εmax.) ,oscillator strength (f
-number) and integrated
absorption coefficient (A)
are taken as indications for
the intensity of transition.

n
 n   n1
A   ( ) d    n1  n 
band 1 2
Oscillator strength (f ): kth
If we regard the molecule as oscillating
dipole then the oscillator strength ( f ) is
defined as the number of virtual oscillators lth kth
equivalent to transitions from lth  kth
electronic state in quantum theory. lth

f  4.32  10 9  
band
( ) d

If the band has Gaussian shape:

 
band
( ) d   ( max )    1
2

  ( max )  ( band width )

f ≥1 Allowed transition
f << 1 , (10-2 – 10-4) forbidden transition
Number of degeneracy = 2J + 1
Where; J is the rotational quantum number
Typical values for energy level separations

10-20 J 10-21 J
-19JJ
10-19
10
 Population of energy states
Population of a state is the average number of molecules
in a state at any time, which may absorb light photons.

At lower temperatures, the lower energy states are more populated. At

higher temperatures, more higher energy states become populated, but
each with less population.
 Effect of energy separation on the population of states

At 300 K kBT ~ 2.5 kJ mol-1.

J =3

J =2 v =1

J =1

J=0 v =0
Example
Assuming that the vibrational energy levels of HCl and
I2 are equally spaced, with energy separations of
2990.94 and 216.51 cm-1 respectively, calculate for each
case the ratio of the number of molecules in the first
two vibrational states relative to the ground state at T =
300 K and 800 K.