Molecular UV-Vis

Spectroscopy

Prof. C. K. Mondal
Department of Chemistry
Jadavpur University
 WHAT IS SPECTROSCOPY?
• Atoms and molecules interact with electromagnetic
radiation (EMR) in a wide variety of ways.
• Atoms and molecules may absorb and/or emit EMR.
• Absorption of EMR stimulates different types of
motion in atoms and/or molecules.
• The patterns of absorption (wavelengths absorbed
and to what extent) and/or emission (wavelengths
emitted and their respective intensities) are called
‘spectra’.
• The field of spectroscopy is concerned with the
interpretation of spectra in terms of atomic and
molecular structure (and environment).
Electromagnetic spectrum
SPECTROSCOPY ‐ Study of spectral information

Physical response Detecting

Molecule
stimulus instrument

Visual (most common)

representation, or
Spectrum

Upon irradiation with infrared light, certain bonds respond by

vibrating faster. This response can be detected and translated
into a visual representation called a spectrum.
 Spectroscopy
• The analysis of the EM radiations emitted, absorbed or
scattered by atoms, molecules or matter
• Photons of the radiation bring information to us about the atom,
molecule or matter.
• The difference between molecular and atomic spectroscopy: a
molecule can make a transition between its electronic,
rotational and vibrational states.
• The rotational and vibrational spectroscopy of a molecule can
provide information about the bond lengths, bond angles and
bond strength in the molecule.
 General features of spectroscopy

hν = | E1 − E2 |
~ 1 ν
ν= =
λ c
ν~ is called the wavenumber of the
photon and gives the number of
complete wavelengths per centimeter. It
is in the unit of cm‐1.

Emission spectrum: A molecule returns to a state of lower energy

E1 from an excited state of energy E2 by emitting a photon.
Absorption spectrum: A molecule is excited from a lower energy
state to a higher energy state by absorbing a photon as the
frequency of the incident radiation is swept over a range
 Stimulated and Spontaneous emissions
Spontaneous emission:
A molecule in an excited state will decay to a lower
energy state without any stimulus from the outside.

Stimulated emission:
As an EM radiation incident upon a molecule in an
excited state can cause the molecule to decay to a lower
energy state. If the incoming photon has the same
frequency as the emitted photon, the incident and
emitted photons have the same wavelength and phase
and travel in the same direction. The incoming photon is
not absorbed by the molecule but triggers emission of a
second photon. The two photons are said to be coherent.

The stimulated emission is the fundamental physical

process of the operation of the laser.
 Raman spectrum

A monochromatic radiation is incident and scattered by the molecule. The

frequency of a scattered radiation is different from the frequency of the
incident radiation. The spectrum of the scattered radiation is called the
Raman spectrum.
Stokes Raman spectrum: The frequency of the scattered radiation is
lower than the frequency of the incident radiation.
Anti-Stokes Raman spectrum: The frequency of the scattered radiation is
higher than the frequency of the incident radiation.
 Transition dipole moment and selection rules
• Transition dipole moment integral
The strength with which individual molecules are able to interact with the EM
radiation and generate or absorb photons. The transition dipole moment
depends on the initial and the final states of the molecules

μ fi = ∫ ψ *f μˆ ψ i dτ μ̂ : Electric dipole moment operator

 The Beer-Lambert law for absorption
The intensity of radiation transmitted by an absorbing sample decreases
exponentially with the path length through the sample.

I
T=
I0
I0
A ≡ log = ε [c ]L
I
I = I 010 −ε [ c ] L
A
[c ] =
ε ⋅L

I0 and I : Intensities of the incident and transmitted radiations

A : Absorbance of the sample, T: Transmittance
L : Length of the sample ε depends on
[c] : Concentration of the absorbing species in the sample wavelength of the
incident radiation.
ε : Molar absorption coefficient or the extinction coefficient
 UV‐Visible Spectroscopy

• THE BEER‐LAMBERT
LAW I ⎛I ⎞
T= t %T = ⎜⎜ t ⎟⎟ x 100
• For a light absorbing Io Io ⎝ Io ⎠
medium, the light

light intensity (I)

intensity falls
exponentially with
Io It
sample depth.
• For a light absorbing l
medium, the light
intensity falls It cuvette
exponentially with
increasing sample
concentration. l Sample depth
 UV‐Visible Spectroscopy

A = ε λ cl A = − log10 T
Absorbance

¾ The negative logarithm of T is called the

absorbance (A) and this is directly
proportional to sample depth (called
pathlength, l) and sample concentration
(c). The equation is called the Beer‐
Lambert law.
ε is called the molar
absorption coefficient
and has units of dm3
Concentration mol‐1 cm‐1
 UV‐Visible Spectroscopy

• Beer‐Lambert Law
limitations
– Polychromatic Light
– Equilibrium shift
– Solvent
– pH
 Rotational energy levels of a rigid rotor
The kinetic energy of a rigid rotor with
angular momentum Jx, Jy and Jz. with respect
to the three principal axes of the rotor.

J x2 J y2 J z2 Classical
E = + +
2Ix 2Iy 2Iz description

For a linear or spherical rigid rotor with a

moment of inertia I

J2
E = , J 2
= J x2 + J 2
y + J z2
2I
~
Quantum E J = hcB J ( J + 1),
ΔE J = E J +1 − E J
description J = 0, 1, 2, 3, ....
~
~ h = 2hcB ( J + 1)
B=
4πcI
 Rotational spectroscopy
• Gross selection rule: The molecules must have a permanent electric dipole
moment so that the molecules are polar.

Classical description Rotational-inactive molecules: Molecules

without rotational spectrum
Homonuclear diatomic molecules: N2, O2
Symmetric linear molecules: CO2
Tetrahedral molecules: CH4
Octahedral molecules: SF6, C6H6

Rotational-active molecules: Molecules

with rotational spectrum
Heteronuclear diatomic molecules: HCl
Less symmetric polar molecules: NH3, H2O

To an observer, a rotating polar

molecule has an electric dipole that
appears to oscillate. This oscillating
dipole can interact with the EM field.
 Specific selection rules for rotational transition
ΔJ = ±1 and ΔK = 0

• Conservation of angular momentum for ΔJ = ±1

Quantum description
A photon is a spin-1 particle. When the molecule
absorbs one photon, the angular momentum of the
molecule must increase to conserve the total angular
momentum, so J increases by one. When the
molecule emits a photon, the angular momentum of
the molecule must decreases, so J decreases by one.

• For symmetric rotors, ΔK = 0

The dipole moment of a polar molecule does not
move when a molecule rotates around its symmetric
axis and, therefore, there is no absorption or
emission of the EM radiation by the rotation of the
molecule about the axis.
Absorption of allowed rotational transitions
A rigid molecule with K=0 makes a
transition from J to J+1

~
ΔE = E J +1 − E J = 2hcB ( J + 1)

~ ~
ν = 2 B ( J + 1) Rigid‐rotor model

• The rotational spectrum consists of a series of lines at frequencies

separated by 2 .B~
• The rotational spectra of gas‐phase samples are microwave spectroscopy.
• We can use the value of obtained from the rotational spectrum to
estimate the bond length of B
~
a heteronuclear diatomic molecule.
 INFRARED SPECTROSCOPY

• Only vibrations that cause a change in ‘polarity’ give rise to

bands in IR spectra – which of the vibrations for CO2 are
infrared active?

O C O
Symmetric stretch
O C O Asymmetric stretch

Bending (doubly
O C O O C O
degenerate)
 INFRARED SPECTROSCOPY

What is a vibration in a molecule?

• Any change in shape of the molecule‐ stretching of bonds,
bending of bonds, or internal rotation around single bonds

What vibrations change the dipole moment of a

molecule?
• Asymmetrical stretching/bending and internal rotation change
the dipole moment of a molecule. Asymmetrical
stretching/bending are IR active.

• Symmetrical stretching/bending does not. Not IR active

 Vibrations of diatomic molecules
Harmonic approximation around the equilibrium

1 ⎛ d 2V ⎞
V (R) = ⎜⎜ ⎟⎟ ( R − R e ) 2 + ⋅ ⋅ ⋅
⎝ dR
2
2 ⎠0

⎛ d 2V ⎞
k f = ⎜⎜ ⎟⎟
⎝ dR
2
⎠0

1
Vhar ( R) =k f ( R − Re ) 2
2 A diatomic molecule has three
1 translational modes, two rotational
En = (n + ) h ω, n = 0,1,2,3,....
2 modes and one vibrational mode.
1/ 2 kf : force constant of the bond,
⎛ kf ⎞ m A mB
ω=⎜ ⎟ , meff = the curvature of the potential at Re
⎜m ⎟ m A + mB
⎝ eff ⎠
 Infrared spectroscopy: Vibrational transitions
• Gross selection rule
The molecule need not to have a permanent dipole moment but
the electric dipole moment of the molecule must change during
the vibration. The rule only requires a change in electric dipole
moment, possibly from zero.

The typical vibrational frequency of a molecule

is about 1013~1014 Hz. The vibrational
spectroscopy of molecules is in the infrared
region, which normally lies in 300 ~ 3000 cm-1.
Homonuclear diatomic molecules are infrared
inactive, because their dipole moments remain
zero as they vibrate.
Heteronuclear diatomic molecules are infrared
Bending motion of CO2 active, because their dipole moments change as
they vibrate.
 Specific selection rules for infrared spectroscopy
1/ 2
Electric dipole moment
~ ~ 1 ⎛⎜ k f ⎞
⎟
Δn = ±1, ΔE = hcv , ν =
2πc ⎜⎝ meff ⎟
⎠

• Molecules with stiff bonds joining atoms

with low masses have high vibrational
wavenumbers.
• The bending modes of a linear molecule
⎛ dμˆ ⎞ are usually less stiff than stretching modes.
μˆ ( x) = μˆ 0 + ⎜ ⎟ x + ⋅ ⋅ ⋅
⎝ dx ⎠ 0 So, the bending modes usually occur at
lower wavenumbers than the stretching
modes in a spectrum.
Transition dipole element
• At room temperatures, almost all molecules
are in their vibrational ground states (n = 0).
μ fi = ∫ ψ *f μˆ ψ i dτ So, the most probable transition is from n =
0 to n = 1.
⎛ dμˆ ⎞
= μ0 + ⎜ ⎟ ∫ ψ *f xˆψ i dτ + ⋅ ⋅ ⋅ • For Δn = 1, the molecule absorbs one
⎝ dx ⎠ 0 photon and, for Δn = -1, the molecule emits
one photon.
Vibration-rotation absorption spectrum
P branch: ΔJ = -1

~ ~ ~
ν P ( J ) = ν − 2BJ

Q branch: ΔJ = 0
~
νQ ( J ) = ~
ν

R branch: ΔJ = +1

~ ~ ~
ν R ( J ) = ν + 2 B ( J + 1)
Vibration‐rotation spectrum of HCl
Each line of the high-resolution
vibrational spectrum of a gas-
phase heteronuclear diatomic
molecule is found to consist of a
large number of closely spaced
components in the order of 10
cm-1, which suggests that the
structure is due to the rotational
transitions accompanying the
vibrational transitions.

•There is no Q branch.
•The lines appear in pair,
because both H35Cl and
H37Cl contribute in their
abundance ratio 3:1.
Vibration-rotation Raman spectrum of CO

ΔJ=‐2 ΔJ=0 ΔJ=+2