Molecular Spectroscopy-1

2012

Dr. P. Vasudeva Nayak,

Visiting Professor,
Department of Chemistry,
Kuvempu University,
Shankaraghatta- 577415,
Shimoga dist.
pvnayak47@yahoo.co.in
Molecular spectroscopy

Introduction
Spectroscopy is the study of the interaction of
matter with the electromagnetic radiation.

Electromagnetic radiation requires no

supporting medium for its transmission and
passes readily through a vacuum.

Electromagnetic radiation is a form of energy

which displays the properties of both particles
and waves.
 Electromagnetic Radiation

The radiation as wave can be characterized by

wavelength (), frequency (), and velocity.

The particle component is called a photon

The energy (E) component of a photon is proportional

to the frequency .
E = hn
where h is Planck’s constant, h=6.626x10-34Js and
n is the frequency in Hertz, Hz (cycles per second).
Electromagnetic Radiation

Tro, Chemistry: A Molecular Approach 5

 Characterizing Waves

• The wavelength, (l) is a measure of the distance

covered by the wave.
– It is the distance from one crest to the next
or the distance from one trough to the next, or the
distance between alternate nodes.

The units are m, micrometer(µm),nm, and Ao.

1nm=10-9m= 10-7cm=10A ; 1A=10-8cm,=10-10m.
µm=10-4cm=10-3nm=10-6m;

Tro, Chemistry: A Molecular Approach 6

 Characterizing Waves
• The frequency, (n) is the number of waves that pass a
point in a given period of time
The number of waves = number of cycles
The units are hertz, (Hz) or cycles/s = s-1
1 Hz = 1 s-1
Other units are: KHz=103Hz; MHz=106Hz

• The total energy is proportional to the frequency of

the waves. E= hn.

Tro, Chemistry: A Molecular Approach 8

 The Relationship Between Wavelength and Frequency

• For waves traveling at the same speed, the shorter the

wavelength, the more is its frequency

• That is , wavelength and frequency of electromagnetic

waves are inversely proportional.

• The velocity of light ‘c’, wavlength, l and frequency, n are

related by: c = l x n

• And
 s  
-1
c m
s
 m 
Tro, Chemistry: A Molecular Approach 9
• Wave number:
• Frequency is a very large number to use. So wave
number is used.
• It is the reciprocal of wave length. It is the number of
waves per centimeter per second.
• = 1/ l ;
• The unit is cm-1; cm-1 is called Kaiser,
kK=1000K=1000cm-1.
• is mainly used in IR spectra
Relation between energy, frequency, velocity &
wave number

c =  × ; 1 Å = 10 –10 m 1 nm = 10 –9 m 1 m = 10 –6 m

Wavenumber =,
Example 1- Calculate the wavelength in nm of red light
with a frequency of 4.62 x 1014 s-1
Given: n = 4.62 x 1014 s-1
Find: l, (nm)

Concept Plan:
n (s-1) l (m) l (nm)
c 1 nm

Relationships:  109 m
l∙n = c, 1 nm = 10-9 m
Solve:
c 3.00 108 m  s -1 7
  14 -1
 6.49  10 m
 4.62 10 s
1 nm
6.49 10 m  9  6.49 102 nm
7
10 m

Tro, Chemistry: A Molecular Approach 12

Practice – Calculate the wavelength of a radio
signal with a frequency of 100.7 MHz

Tro, Chemistry: A Molecular Approach 13

Practice – Calculate the wavelength of a radio
signal with a frequency of 100.7 MHz
Given: n = 100.7 MHz
Find: l, (m)

Concept Plan:
n (MHz) 6 -1
n (s-1) c l (m)
10 s 
Relationships: 1 MHz 
l∙n = c, 1 MHz = 106 s-1
Solve:
106 s -1
100.7 MHz   1.007 108 s -1
1 MHz
c 3.00 108 m  s -1
  8 -1
 2.98 m
 1.007 10 s
The wavelength is appropriate for radiowaves.

Tro, Chemistry: A Molecular Approach 14

 Example.2- Calculate the number of photons in a laser
pulse with wavelength 337 nm and total energy 3.83 mJ
Given: l = 337 nm, Epulse = 3.83 mJ
Find: number of photons

Concept Plan: number

l(nm) l (m) Ephoton E pulse
109 m hc photons
E photon 
Relationships: 1 nm  E photon
E=hc/l, 1 nm = 10-9 m, 1 mJ = 10-3 J, Epulse/Ephoton = # photons
Solve:
2 109 m
3.37 10 nm   3.37 107 m
1 nm

E photon  
 
hc 6.626 1034 J  s 3.00 108 m  s -1
 5.8985
 10 19
J
  7
3.37 10 m 3.83 10 3 J
number of photons 
3
10 J 3 5.8985  10 3 J
3.83 mJ   3.83 10 J
1 mJ  6.49  1015 photons
Tro, Chemistry: A Molecular Approach 15
Practice – What is the frequency of radiation
required to supply 1.0 x 102 J of energy from
8.5 x 1027 photons?

Tro, Chemistry: A Molecular Approach 16

What is the frequency of radiation required to supply
1.0 x 102 J of energy from 8.5 x 1027 photons?
Given: Etotal = 1.0 x 102 J, number of photons = 8.5 x 1027
Find: n

Concept Plan: number

Ephoton n (s-1)
photons E total E photon
number of photons 
Relationships: h
E=hn, Etotal = Ephoton∙# photons
Solve:
1.0 102 J
E photon   1.176 1026 J
8.5 1027


E photon

1.176 10   1.8 10
26
J 7 -1
s
h 34
6.626 10 Js

Tro, Chemistry: A Molecular Approach 17

 Solved problems

• Calculate the energy in J per quantum(per photon), calories per mole & eV
of radiation of 3000A wavelength.
Solution: E= hn; E = hc/ l. h= 6.26x10-34Js; c= 3x108ms-1.

Ans. E= 6.62x10-19J; Energy per mole=3.95x105J mol-1. = 4.13eV.

The Electromagnetic Spectrum
 Molecular Energy Levels
• Molecules can have the following types of energy
Translational (Kinetic, due to motion)
Electronic (PE and KE of electrons)
Vibrational (oscillation of atoms in bonds)
Rotational
• Translational energy is small and ignored.
•
• Hence, total energy of molecule is:
Emolecule = Erotational + Evibrational + Eelectronic

• Except the translational, all energy levels are quantized

20
 Different types of energy
• Rotational energy: Erot. .

• This is due to “end-to-end” rotation of the whole

molecule along its molecular axis. There are no
change in the bond length during rotation.

• Rotational energy is given by:

• Erot= ½ I w2 where, I = moment of inertia,
w= angular velocity of the rotating molecule.
• I = µr2 where µ= reduced mass given by:

• where m1+m2. are the masses of the two atoms

forming the covalent bond.
• From Quantum mechanics, rotational energy is given
by:

• Rotational energy correspond to microwave region, 1-

100cm-1.

• Polar gaseous molecules like CO, HCl etc absorb

microwave radiation.
• Vibrational energy, Evib:

• It is due to the vibrations (oscillations) of atoms of

the molecule.
• From quantum mechanics, vibrational energy is given
by:
• Evib. = (v +1/2) hn,
where h = Plank’s constant, n = vibrational frequency,
v = vibrational quantum number with values 0, 1, 2,
3, etc.
• Vibrational energy corresponds to IR region, 500-
4000cm-1.

• Polar molecules such as H2O, CO2 etc. absorb IR

radiations.

• There must be a change in dipole moment during

vibrations for IR absorptions.
Molecular vibrations
• Electronic energy, Eelc.:
• Electrons posses energy due nuclear attractions
which are quantized.
• Energy difference between quantized elctronic levels
falls in the VIS region, 10,000- 25,000cm-1, & 25,000-
70,000cm-1 in UV- region
• E= hn, where h= Plank’s constant , n = frequency of
UV-VIS radiation

• Eelc >> Evib >> Erot .

Molecular Energy Levels

28
The IR Spectroscopic Process As a covalent bond oscillates – due to the
oscillation of the dipole of the molecule – a varying electromagnetic field is
produced

The greater the dipole moment change through the vibration, the more intense the EM
field that is generated
 Molecular Energy Levels

The relative energy of the spacings between energy levels

for various types of transitions in a molecule are in the
order:

Rotational Vibrational Electronic Transition

Transition << Transition << 10000-50000 cm-1
1-20 cm-1 2000-4000 cm-1

Thus the various types of energy transitions occur in

different regions of the EMR spectrum and do not overlap

30
 Molecular absorption processes
~10-18 J
• Electronic transitions
• UV and visible wavelengths

• Molecular vibrations
Increasing energy
• Thermal infrared wavelengths

• Molecular rotations
• Microwave and far-IR wavelengths
~10-23 J

• Each of these processes is quantized

 Absorption of radiation

• Interaction of radiation with matter:

• Absorption occurs if the radiation energy matches
the energy gap between the quantized energy levels
of the molecule.
• If not the molecule is transparent to the radiation.
• Absorption of radiation may cause the following
changes:
• 1. Rotational energy levels - microwave radiation.
• 2. Vibrational energy levels - IR radiation
• 3. Electronic energy levels - UV-VIS radiation
• 4. Nuclear energy levels - Raido frequency.
Interaction of radiation with matter

Wavelength
 X-ray interactions

• Quantum energies of x-ray photons are too high to be absorbed by electronic

transitions in most atoms - only possible result is complete removal of an electron
from an atom

• Hence all x-rays are ionizing radiation

• If all the x-ray energy is given to an electron, it is called photoionization

• If part of the energy is given to an electron and the remainder to a lower energy
photon, it is called Compton scattering
 Ultraviolet interactions

• Near UV radiation (just shorter than VIS) is absorbed very strongly in the surface
layer of the skin by electron transitions
• At higher energies, ionization energies for many molecules are reached and the
more dangerous photoionization processes occur
• Sunburn is primarily an effect of UV radiation, and ionization produces the risk
of skin cancer
 Visible light interactions

• Visible light is also absorbed by electron transitions

• Higher energies at blue wavelengths relative to red wavelengths: hence

red light is less strongly absorbed than blue light

• Absorption of visible light causes heating, but not ionization

• Car windshields transmit visible light but absorb higher UV frequencies

 Infrared (IR) interactions

• Quantum energy of IR photons (0.001-1.7 eV) matches the ranges of quantized

vibrational energy levels in molecules
• Vibrations arise as molecular bonds behave like springs.
 Microwave interactions

•
• Quantum energy of microwave photons
(0.00001-0.001 eV) matches quantized
rotational energy levels in molecules.

• Absorption of microwave radiation

causes heating due to increased
molecular rotational activity

• Most matter transparent to µ-waves,

microwave ovens use high intensity
µ-waves to heat material
 Type of quantum
Radiation Type of spectroscopy transition

-ray Nuclear
-rays
emission

X-rays Electronic
X-rays
Absorption, (Inner shell)
emission
UV UV-absorption
Electronic
Energy

UV-VIS
absorption, (Outer shell)
VIS
emission
IR-absorption Molecular
IR Raman Vibration
rotation
Micro- Microwave
Molecular
wave Absorption
Rotation

Magnetically
Radio NMR EPR Induced
Spin states
Electromagnetic spectrum
 Absorption of Radiation
• Absorption of energy promotes molecules from
ground state to one or more higher energy states.

• The energy of the exciting photon must exactly match

the energy difference between the ground state and one
of the excited states of the absorbing species.

• Since these energy differences are unique for each

species, a study of the frequencies of absorbed radiation
provides a means of characterizing the molecules.