3rd year Spectroscopy 3rd year spectroscopy: 1st Topic

Dr. Alan Ryder (R222, Physical Chemistry)
General Features of Spectroscopy:

– Introduction & review of 2nd year.

4 lectures:
– Transitions & probabilities.
– Rotational & Vibrational spectroscopies – Populations of energy levels & consequences.

1 exam question. – Linewidths.
– Bohr Condition.

Notes on:
– www.nuigalway.ie/nanoscale/3rdspectroscopy.html

Be able to show an understanding of the theories behind

Spectroscopy links on: spectroscopy. Be able to calculate populations of energy levels and
– http://www.nuigalway.ie/nanoscale/links.html spectral line widths.
– Section 8.1-2, Physical Chemistry, Atkins 8th ed., p.243.

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Introduction-General Principles Absorption spectroscopy

Spectra - transitions between
energy states:
– Molecule, Ef - Ei = hν (photon
energy).

Transition probability:
– selection rules.

Populations (Boltzmann
distribution).

Molecules have bonds they
BEFORE
can vibrate…

Wavenumber: 5000 nm = 5
x10-4 cm = 2000 cm-1
∆E (molecule) = E
Can refer to the absorption of any frequency of radiation,
most common are:
(photon)
– UV-visible absorption (electronic).
– IR absorption (vibrational).
ENERGY – Microwave absorption (rotational).
PHOTON – NMR/ESR (nuclear & electron spin).

These are many types of molecular spectroscopy.
DURING AFTER
Energy of the radiation ≅ energy of transition.

Based on quantum principles.
ε =hν =hc/ λ =hcν

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1
 Emission & Scattering spectroscopy

EMISSION: Emission of any
frequency of radiation.

Concerned with the properties
of the emitted photons from a
sample.

In the UV-VIS-NIR
(electronic transitions ):
– Fluorescence, Phosphorescence,
Chemiluminescence,
photoluminescence,

In the Microwave:
– Rotational transitions,
astrophysics.

Based on quantum principles.

SCATTERING: Look at how
light scatters from
molecules/materials:
– Not absorbed, photons don’t
have to pass thru
– Can use everything from
neutrons to x-rays etc.

Most Important is Raman
spectroscopy:
– Molecular technique.
– Great for forensics etc.
Intensities of spectral lines

Three Essential concepts govern intensity:

Transition probability: the likelihood of a system (e.g.
molecule) changing from one state to another.

Population of Energy levels: the number of molecules (or
atoms in the initial state).

Concentration (& path length): The amount of material
present giving rise to the spectrum.
– This done last year: Beer-Lambert

5 6

Transition probability (I): Transition probability (II):

Based on quantum mechanical principles…..is a transition
allowed or forbidden?

To simplify matters we use selection rules.

Each type of spectroscopy has it’s own selection rules.

Underlying classical idea:
– for a molecule to be able to interact with the EM field and
absorb or create a photon of frequency ν,
– it must possess, at least transiently, a dipole oscillating at that
frequency.
Transition dipole moment : µz,f i = ∫ Ψ *f µˆ z Ψ i dτ .
Ψ i = wave function of the initial energy state.
Ψ f = wave function of the final energy state.
µˆ z = is the electric dipole moment operator.
Rate of change of population of the state Ψ f (w f ←i ) due to transitions from
state Ψ i is: w f ←i ∝ |µz,f i |2Ε 2 where E = amplitude of EM field, ∝ intensity.
The size of the transition dipole can be regarded as a measure of the
charge redistribution that accompanies a transition.
A transition will be active (and generate or absorb photons)
only if the accompanying charge redistribution is dipolar.

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2
 Transition probability (III):

1s electron → a 2s electron:
– Spherical migration of charge.
– No dipole moment assoc. with this
charge migration.
– Transition is electric-dipole forbidden.

1s electron → a 2p electron:
– Dipole associated with the charge
migration.
– This transition is allowed.
Gross Selection Rules

Specifies the general features a molecule must have if it is
to have a spectrum of a given kind:
– e.g. a molecule gives a rotational spectrum only if it has a
permanent electric dipole moment.
– e.g. a vibration is Raman active only if there is a change in
polarizability.

A detailed study of the transition moment leads to the
specific selection rules that express the allowed
transitions in terms of the changes in quantum numbers.

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Populations of energy levels (I) Populations of energy levels (II)

The strength of an absorption depends on the number of molecules
In spectroscopy:
in a particular energy level. – interested in the relative populations of energy levels.

Governed by the Boltzmann Distribution: N i ∝ g i × e- Ei /kT at equilibrium, where g i = number of degenerate levels.
Ni e- Ei /kT
Ne- Ei /kT ⇒ ratio = = gi × , q = partition function
Boltzmann distribution: N i = , q = partition function N q
q
Nf g e- Ef /kT N g
⇒ ratio = = f × - E /kT , rearrange to: f = f × exp( −( E f − Ei ) / kT ) ,
N i = no. molecules in an energy level, i, with energy E i . Ni gi e i Ni gi
N = total no. molecules in system. N i = no. molecules in an initial energy level, i, with energy Ei .
Taking into account degenerate energy levels, we can write: N f = no. molecules in a final energy level, f , with energy E f .

N i ∝ g i × e- Ei /kT at equilibrium, N f  final state 

So assuming single states: = exp(−(∆E ) / kT ),
Ni  initial state 
where g i = number of degenerate levels.

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3
 Typical energies & populations Spectroscopic Consequences
Region Frequency NA hυ nf / ni
For RF (NMR) & Microwave (Rotational):
(Hz) – Energies are very low (∆E’s small).
– Population differences are small ⇒
– Easy to saturate the energy levels.
RF 10 7 4 mJ/mol 0.999998

When molecules are heated up:
Microwave 1011 40 J/mol 0.984 – Higher E levels are populated ⇒
IR 13 4 kJ/mol
10 0.202 – More allowed transitions, more complex spectra.
15 – Tends to a continuum fairly easily.
UV-VIS 10 400 kJ/mol 3x10-70

For large ∆E’s, ground state is the most populated.
X-RAY 1018 400 MJ/mol <10-99

13 14

Fate of molecule? Linewidths

Non-radiative transition: M* + M → M + M + heat

Spontaneous emission: M* → M + hν (very fast for large ∆E)

Stimulated emission (opposite to stimulated absorption).
These factors contribute to linewidth & to lifetime of excited state.

A number of effects contribute to the widths of
spectroscopic lines.

Some contributions to linewidths can be modified by
changing the conditions:
– To achieve high resolutions we need to know how to minimize
these contributions.

Other contributions cannot be changed:
– Represent an inherent limitation on resolution.

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 Linewidths: Doppler Broadening Linewidths: Doppler Broadening (I)

One important broadening process in gaseous samples is
When a source emitting electromagnetic radiation of frequency ν
the Doppler effect: moves with a speed s relative to an observer, the observer detects
radiation of frequency:
– Radiation is shifted in frequency when the source is moving
towards or away from the observer.

Very important for the study of gaseous samples: 1/ 2 1/ 2
 1− s / c   1+ s / c 
– Atmospheric & interstellar chemistry. ν receeding = ν   ν approaching = ν   where
– In some cases, meaningful spectroscopic data can be obtained  1+ s / c   1− s / c 
only from gaseous samples. c = speed of light, s = speed of source. For s << c, then:
ν ν
ν receeding ≈ , and ν approaching ≈ ,
1+ s / c 1− s / c

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Linewidths: Doppler Broadening (II) Linewidths: Doppler Broadening (III)

As temperature increases:
Molecules reach high speeds in all directions in a gas:
– Molecules speed up. – stationary observer detects the corresponding Doppler-shifted
– Line broadens. range of frequencies.

Very significant in astrophysics. – Some molecules approach the observer, some move away; some

To solve this: move quickly, others slowly.

Make measurements @ very low
The detected spectral ‘line’ is the absorption or emission
temp.
profile arising from all the resulting Doppler shifts.
– Liquid N2 (-196 ºC)
– Liquid He (-270 ºC)

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 Linewidths: Doppler Broadening (IV) Linewidths: Doppler Broadening (V)
- Ei /kT
Ne
We know from the Boltzmann distribution: N i =
q
, q = partition function −mc 2 (ν − ν ) 2 / 2ν 2kT

)
Iν ∝ e obs ...Gaussian Function.
The probability that a gas molecule of mass m & speed s in a sample with temp. T obs
1 2 e- ms Linewidth at half-height can be calculated and gives:
has Kinetic Energy, E K = ms is proportional to .
2 2kT 1/ 2 1/ 2
2v  2kT ln 2  2λ  2kT ln 2 
We can relate this to the observed frequencies: ν obs ≈ ν 
 1 
,
δν obs =   or δλobs =  
 1± s / c  c  m  c  m 
When s
c, the Doppler shift in the frequency is ν obs - ν ≈ ±ν s/c Better to write......
⇒ a symmetrical distribution of observed frequencies w.r.t. molecular speeds. 1/ 2 1/ 2
Intensity I of a transition at ν obs : δν obs 2  2kT ln 2  δλobs 2  2kT ln 2 
=   or =  
∝ probability of finding molecule that emits/absorbs at ν obs , v c m  λ c m 

− mc 2 (ν − ν ) 2 / 2ν 2 kT T
⇒ I ν obs ∝ e Always remember: line width ∝
(

obs .....Gaussian Function

m

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Linewidths: Doppler Broadening (VI) Doppler Broadening: example (I)

For light masses & high temperatures: A fluorescent molecule emits red light at 660 nm. What is the Doppler-shifted
– Broad lines ⇒ cool the system for higher resolution. wavelength if it is approaching approached at 80 km hr −1?
At what speed of approach would it appear green (520 nm)?

For a molecule like N2 at r.t. (T ≈ 300 K):
ν
– δν/ν ≈ 2.3 × 10−6. Step 1: Equations: ν approaching ≈ , c=speed of light, s=speed of source.
1− s / c
– For a typical rotational transition 1 cm−1 (ν = 30 GHz),
1  s
– linewidth ~ 70 kHz. Step 2: Rearrange: We know: ν ∝ ⇒ λOBS = 1 −  λ
λ  c
– ∆λ = 2.3 µm (what was the wavelength?) 80 km h −1 = 22.222 ms −1
 22.222 ms −1 
⇒ λOBS = 1 − −1 
660 nm = 0.999 999 925 × 660 nm
 2.998 ×10 ms 
8

λOBS = 659.9999505 nm

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6
 Doppler Broadening: example (II) Linewidths: Lifetime Broadening (I)
At what speed of approach would it appear green (520 nm)?
Spectroscopic lines from gas-phase samples are not infinitely sharp
 s even when Doppler broadening has been largely eliminated by
Step 3: Rearrange: λOBS = 1 −  λ working at low temps:
 c – Same is true of the spectra of samples in condensed phases and solution.
 λ 
This residual broadening is due to quantum mechanical effects.
⇒ s = 1- OBS  c
 λ 
Specifically, when the Schrödinger equation is solved for a system
Step 4: Input values: that is changing with time, it is found that it is impossible to specify
the energy levels exactly:
 520 × 10−9 m  −1 −1 – Heisenberg again….
s =  1- −9  2.998 × 10 ms = 6.366 × 10 ms
8 7

 660 × 10 m 
These kinds of speed found in interstellar space......
Allows astronomers to calculate velocities of systems.

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Linewidths: Lifetime Broadening (II) Lifetime Broadening (example)

If on average a system survives in a state for a time τ (tau), the Estimate the lifetime of a state that gives rise to a line of width of:
lifetime of the state:
(a) 0.10 cm −1 , (b) 1.0 cm −1 , (c) 100 MHz.
Then its energy levels are blurred to an extent of order δ E, where: 5.3 ( cm −1 ) 5.3 ( ps )
 Step1: Equations: δν ≈ , rearrange to: τ ≈
δ E= aka.....uncertainty broadening τ (ps) δν
τ 5.3 ( ps ) 5.3 ( ps )
Can express in terms of wavenumber: [Rem. E=hcν ] (a) : τ (ps) ≈ = 53 ps (b) : τ (ps) ≈ = 5.3 ps
0.10 cm −1 1.0 cm −1
5.3 ( ? ) ν (s −1 )
δ E = hcδν, ⇒ δν ( cm −1 ) = [Work it out ] (c) : Convert MHz to cm -1 : hcν = hν ⇒ ν =
τ (in ps) c(cms −1 )
Long lifetime ⇒ small uncertainty ⇒ narrow linewidths 100 × 106 (s −1 ) 5.3 ( ps )
ν = = 0.0033 cm −1 ⇒ τ (ps) ≈ =
Short lifetime ⇒ larger uncertainty ⇒ wider linewidths 2.998 × 1010 (cms −1 ) 0.0033 cm -1
τ = 1.6 × 10−9 s = 1.6 ns

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 3rd year spectroscopy: 2nd Topic Background

Pure Rotational Spectroscopy:
Widely used in astronomy to study the molecular
– Microwave spectroscopy. composition of interstellar clouds.
– Moments of inertia and angular momentum. – Rotational motions ⇒ low energies ⇒ long wavelengths
– Rotational Energy levels & populations of E levels. – Microwaves………long pathlengths
– Degeneracy & selection rules.
– NASA website: http://dsnra.jpl.nasa.gov/IMS/
– Selection rules.
– Centrifugal distortion.
Interstellar molecules:

Understand and be able to explain rotational
H2O, CO, CS2, NH3, H2CO, CH3OH…..etc.
spectroscopy, calculate energy levels and energies of
Biggest molecular spectrometers……
spectroscopic transitions.
– Section 8.3-8.7, Physical Chemistry, Atkins 8th ed., p.254.
– Section 19.5-19.7, Elements of Physical Chemistry, 4th ed.

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Sample spectrum (mixture) Microwave spectrometer

VACUUM

MICA WINDOW BRASS TUBING

MCWE
DETECTOR
SOURCE

100 kHz
OSCILLATOR AMPLIFIER

FREQUENCY
DISPLAY
SWEEP

Microwave 3 to 60 GHz:
– X-band at 8 to 12 GHz; wavelength = 25-35 mm

Very Sharp absorption/emission lines in GHz range.
Path-length 2 m; pressure 10-5 bar; Temp to 800 K;
– vapour-phase.

Each molecule has different bands.

Mica windows: transparent to MCWE

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8
 Microwave spectroscopy Moment of Inertia (I)

Low pressure to avoid molecular collisions.
KEY PARAMETER.

Compounds must be in the vapour-phase
Rotational inertia
– But it is easy to work at temperatures up to 800 K since cell is
Rotational analogue of mass for
made of brass with mica windows. Even solid NaCl has linear motion
sufficient vapour pressure to give a good spectrum.
I must be specified with respect

Very high-resolution e.g. 12C16O absorption at to a chosen axis of rotation
115,271.204 MHz
For a point mass:
– Can be used to identify compounds – I = mr2.

Rotation ⇒ Moments of inertia
– Will give information about bond lengths and bond angles.

33 34

Moments of inertia Asymmetric Rotors:

Key molecular parameter: the
This is the most complex
moment of inertia, I, of the case…very difficult to solve.
molecule.
Three different moments of

Defined as the mass of each inertia; IA≠ IB ≠ IC
atom multiplied by the square
all three rotation axes coincide
of its distance from the at the centre of mass of the
rotational axis through the molecule.
centre of mass of the molecule.
Examples;
– Water

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 Moments of Inertia (I) Moments of Inertia (II): Spherical

Relatively Simple terms:

Tetrahedral (e.g. CH 4 )
8
I= mA R 2
3

Most important cases (3Y): linear diatomic & triatomic molecules. Octahedral (e.g. SF6 )
I = 4mA R 2

37 38

Rotors & other definitions Moments of Inertia (III): Symmetrical

Rigid Rotor: a body that does not distort under the stress Complex forms:
of rotation.
2 different

Linear rotor: a rigid rotor with one moment of inertia orientations.
equal to zero (e.g. CO2, HCl, OCS, and HC≡CH).

Spherical rotor: a rigid rotor with three equal moments .
of inertia (e.g. CH4, SiH4, SF6).

Symmetric rotor: a rigid rotor with two equal moments of
inertia (e.g. NH3, CH3Cl, and CH3CN).

Asymmetric rotor: a rigid rotor with three different
moments of inertia (e.g. H2O, H2CO, and CH3OH).

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10
 What type of spectra? Energy Levels for rotating systems

Based on moments of Classical case: energy of a body rotating about an axis a is:
inertia, I = mr2: 1
Ea = I aωa2 , ωa = angular velocity (rad s-1 ) about that axis,

IA = IB = IC 2
– no MCWE spectrum e.g. Ia = moment of inertia and
CH4 1 1 1

IA = 0, IB = IC In 3D: E = I aωa2 + I bωb2 + I cωc2 ,
2 2 2
– linear molecules e.g. NaCl angular momentum about axis a is J a = Iaωa , ⇒

IA ≠ IB = IC
J a2 J b2 J c2
– complicated e.g. NH3 E= + + , This is the key equation.
2I a 2Ib 2Ic

IA≠ IB ≠ IC
– very complex e.g. H2O Use this and quantum mechanics to obtain rotational energy levels.
Start with 2D case:

41 42

Rotation: system conditions (2D) Angular Momentum

Body of mass m confined to a ring of radius R by V=0
Angular momentum Jz = ± pr (p = mv)

XY plane only – Momentum × Radius
– ± term because you can have two different directions
– Clockwise, Anti-clockwise
Total Energy = Kinetic energy (E k )

Right Hand Rule:
E k = ½ mv 2 – Fingers point in direction of travel
Rem: Momentum, p = mv – Thumb points in Jz direction
p2
⇒ Ek =
2m
BUT....not linear motion...so:

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11
 Rotational Energy: Rotational Energy:
J z2 J z2
Ek = , mr 2
= I (moment of inertia ) so ⇒ Ek = ....... 2π r hr
2mr 2 2I λ= , and Angular Momentum: J z = ±
What values allowed?...NOT ALL. ml λ
h hr ml h
de Broglie: λ = , and J z = ± pr , ⇒ J z = ± ⇒ Jz = = ml  ml = 0, ±1, ±2 [Quantisation]
p λ 2π
ψ (0)=ψ (2π ) otherwise: ( ml  ) , m = 0, ±1, ±2
2
J z2
destructive interferance. Remember: Ek = 2
, ⇒ Ek = l
2mr 2mr 2
λ can only have certain values:
2π r
ml2 2
⇒λ = , ml = 0,1, 2, 3 ∴E = , ml = 0, ±1, ±2.....Remember: I = mr 2
ml k 2I

45 46

Energy Levels 3D Rotational Constants

Can easily extend to 3D and get:
Coefficients of quantum numbers in the rotational term
expression and inversely proportional to the principal
EJ = J ( J +1) ,
2
J = 0,1, 2,3..... moments of inertia.
2I
mJ = ± J , ± ( J − 1), ± ( J − 2)........0 h2
B= , units in Joules (J)
J = rotational Quantum number, 8π 2 I
mJ = subsiduary quantum number.  = h
B , units in wavenumber (cm -1 ).
NOTE: Energy depends on Moment of Inertia. 8π cI 2

h is Planck's constant & c the speed of light in vacuum.

Always check the units to see which B expression used
[SI units preferred].

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12
 Energy levels:
Spherical rotors (e.g. CH 4 ):
E J =BJ(J+1), J=0,1,2,3.............
Seperation between adjacent levels: E J − E J-1 = ∆E = 2BJ
Linear rotors (e.g. CO 2 , HCl, C2 H 2 ):
E J =BJ(J+1), J=0,1,2,3.............
Seperation between adjacent levels: E J − E J-1 = ∆E = 2BJ
Rotational constant decreases as I increases ⇒
large molecules have closely spaced rotational E levels.
49
Degeneracy

Degeneracy of Jth level is (2J+1)
– mJ subsidiary quantum number
– angular momentum of the molecule has a
component on an external, lab.-fixed axis (z)
– (a) MJ is close to its maximum value, J, most of
the molecular rotation is around the laboratory z-
axis.
– (b) An intermediate value of MJ.
– (c) When MJ = 0 the molecule has no angular
momentum about the z-axis.
– All three diagrams correspond to a state with K
= 0.
51
Energy levels: symmetric Rotor
In symmetric rotors, two moments of inertia are equal but different
from the third (as in CH3Cl, NH 3 , and C6 H 6 );
the unique axis of the molecule is its principal axis.
Now energy term is more complex (see Atkins for details) :
EJ ,k = BJ ( J +1) + ( A − B) K 2 , J = 0,1,2,3...K = 0, ±1, ±2...
K is the quantum number used to signify
a component on the principal axis;
angular momentum about the principal axis,
50
Degeneracy & Stark effect:

Polar linear rotor case:
– Can observe the degenerate energy
levels by applying an external electric
field MJ = 0 :
– All sublevels are doubly degenerate
except that with MJ = 0

2J+1 fold degeneracy:
– E.g. J =7, 15 levels.
52
13
 Rotational energy levels: Linear Rotor Selection Rules (1):

For ∆ J=1:
Selection rules for absorption are:

∆E = 2 (J) h2/8π2I J=4, M4=9
The molecule must have a non-zero
– 0→1: ∆E = 2 h2/8π2I dipole moment, µ ≠ 0.
– 1→2: ∆E = 4 h2/8π2I – A rotating polar molecule looks like an
– 2→3: ∆E = 6 h2/8π2I oscillating dipole that can stir the EM field
J=3, M3=7
etc., E into oscillation (and vice versa for
absorption).

Rem. J= upper E level.
∆J = +1

Constant increasing
J=2, M2=5
difference of:
J=1, M1=3
– ∆E = 2 h2/8π2I = 2B
0 J=0, M0=1

53 54

Selection Rules (2): Selection Rules (3):

Rotational Inactive molecules:
– Homonuclear diatomics: N2, O2, etc.
– Symmetrical linear molecules: CO2.
– Spherical rotors (CH4) cannot have electric dipole
moments.

Which of the following molecules are rotationally
active and yield a pure rotational spectrum?

CO2, OCS, H2O, CH2=CH2,

C6H6, H2, NO, N2O, CH4

Specific rotational selection rules are found by
evaluating the transition dipole moment between
rotational states.
– ∆J = ±1, ∆MJ = 0, ±1
– ∆J = +1 corresponds to absorption.
– ∆J = −1 corresponds to emission.

The allowed change in J in each case arises from
the conservation of angular momentum when a
photon, (a spin -1 particle), is emitted or absorbed.

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14
 Rotational energy levels: linear rotor. Example 1:(I)

Top: transitions allowed by The splitting between the spectral lines in the 12C16O
the selection rule ∆J = ±1, spectrum is 3.8626 cm-1. Find the value of re, the

Bottom: typical pure equilibrium internuclear distance.
rotational absorption spectrum 2h 2
(displayed in terms of Step 1: Equations: ∆E = , for a linear diatomic: I = µr 2 .
8π 2I
transmitted radiation).
Intensities reflect: 2h2 2h2 2h2

Rearrange to : ∆E = ⇒ r 2
= ⇒ r =
– populations of the initial level. 8π 2 µr 2 8π 2 µ∆E 8π 2 µ∆E
– strengths of the transition dipole
moments.
Step 2: Calculate reduced mass for 12 C16 O:

Constant frequency separation.
µ=
mC mO
,µ =
( 0.012)( 0.016) × 1 kg, N = avogadros number

Increasing energy separation. mC + mO ( 0.012) + ( 0.016) Na a

µ = 1.139 x 10-26 kg

57 58

Example 1:(II) Appearance of spectra

Step 3: Convert cm -1 to joules:ν = 3.8626 cm -1 , ∆E = hcν

Intensities of spectral lines increase with
⇒ ∆E = (6.621×10−34 Js) × (2.998 ×1010 cms −1 ) × (3.8626 cm −1 ) increasing J and pass through a max. before tailing
∆E = 7.667 ×10−23 J off as J becomes large.
Step 4: input values:

The most important reason for the maximum in
2h 2 2 × (6.626 ×10−34 Js) 2 intensity is the existence of a maximum in the
re = =
8π 2 µ∆E 8π 2 × (1.139 ×10−26 kg) × (7.667 ×10−23 J)
population of rotational levels.
8.768 ×10−67 J 2s 2 )
re = = 1.272 ×10−20 Jkg -1s 2 [REM: 1 J= 1 kgm 2s -2 ]
Boltzmann distribution implies that the population
6.895 ×10−47 kgJ
of each state decays exponentially with increasing
o
re = 1.128 ×10−10 m = 1.128 Α J, but the degeneracy of the levels also increases.

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 Populations of rotational levels Relative populations

nJ ∝ gJ e(
−ε J / kT )
Thermal equilibrium
Use this to calculate relative populations of rot.
J 2J+1 exp ( -εε / kT ) nJ / n0 the relative E levels for linear rotor.
0
1
1
3
1.000
0.981
1.00
2.94
populations of the
REMEMBER:
2 5 0.945 4.73 energy levels…
You have to have
3 7 0.893 6.25
4 9 0.828 7.45
molecules in the ground
5 11 0.754 8.29
Show how state… AND…
6 13 0.673 8.75
7 15 0.590 8.85 spectra/populations
a vacancy in the excited
8 17 0.507 8.62 state for absorption…
9 19 0.428 8.13 change with
temperature &
Like airlines….
energy.
61 62

Example (2): part I Example (2): part II

Pure Microwave absorptions at 84.421, 90.449, and 96.477 GHz on 2 h2
flowing dibromine gas over hot copper metal at 1100 K. ∆E = = hν = h(6.028 ×109 s -1 )
8π 2 I
What transitions do these frequencies represent?
2 h2 2 h2
What is the bond length of the species formed? Assume linear rotor. Rearrange to : I = =
8π 2 ∆E 8π 2 (h × 6.028 ×109 s -1 )
Step1 Analysis: 96.477 - 90.449 = 6.028 & 90.449 - 84.421 = 6.028
2 (6.626 ×10-34 Js)
So, constant near constant differance: 6.028 GHz = 6.028 × 109 s -1. I= = 2.784 × 10-45 Js 2 (= kgm 2 )
8π 2 (6.028 × 109 s -1 )
⇒ 84.421 ÷ 6.028 = 14 J=13 → J=14 ⇒ ∆E = 28B
(0.063 × 0.079)
⇒ 90.449 ÷ 6.028 = 15 J=14 → J=15 ⇒ ∆E = 30B I =µ r 2 , µ = N A = 5.82 × 10-26 kg
(0.063+0.079)
⇒ 96.477 ÷ 6.028 = 16 J=15 → J=16 ⇒ ∆E = 32B
 h  2 2.784 × 10-45 kgm 2
∆E = 2BJ = 2  2  J = hν ⇒ 2B = h (6.028 × 109 s -1 ) . ⇒ r= I/µ = = 218.6 ×10-12 m.
 8π I  5.82 × 10-26 kg

Data from NIST website, Original paper: Manson, De Lucia, Gordy. J. Chem. Phys. 63, 2724 (1975). 63 64

16
 Centrifugal distortion (I) Centrifugal distortion (II)

Atoms of rotating molecules are
Increased bond lengths ⇒ bigger moments of inertia
subject to centrifugal forces – reduces the rotational constant

– tend to distort the molecular geometry
– changes the moments of inertia

The effect of centrifugal distortion on a
diatomic molecule is:

⇒ stretch the bond

⇒ increases the moment of inertia.

consequently the energy levels are slightly closer than the rigid-
rotor expressions predict.

Effect is usually taken into account empirically by subtracting a
term from the energy and writing:
E ( J ) = BJ ( J + 1) − DJ J 2 ( J + 1)2
D J is the centrifugal distortion constant.
D J is large when the bond is easily stretched.

65 66

Emission spectroscopy: 1 3rd year spectroscopy: 3rd Topic

Radio-telescopes pick up radiation from interstellar space.
High resolution means that species can be identified
unambiguously.

Owens Valley Radio Observatory 10.4 m telescope

Orion A molecular cloud ~300K, ~10-7 cm-3

517 lines from 25 species

CN, SiO, SO2, H2CO, OCS, CH3OH, etc

13CO (220,399 MHz) and 12CO (230,538 MHz)

See spectrum on slide 35.

Vibrational Spectroscopy:
– Introduction & selection rules.
– Potential energy level diagram.
– Anharmonicity
– Morse Potential Energy curve.
– Overtones & Hot bands.

Understand and be able to explain vibrational spectroscopy, terms
and concepts. Calculate reduced masses, energy levels &
transitions, force & anharmonicity constants, & number of
vibrational modes.
– Sec. 19.9-19.15: Elements of Physical Chemistry, 4th ed.
– Sec. 13.9-13.15: Physical Chemistry, 8th ed. Atkins.

67 4th year QChem 68

17
 Molecular vibrations 1 Molecular vibrations 2

All molecules capable of vibrating.
Observing the frequencies of vibration can be used to ID molecules:

Many different types of vibration (modes)|: Molecular Fingerprints
– Stretching, Bending, Wagging, Twisting.
FT-IR and Raman spectroscopy used in this way for:
– Forensics (drugs, explosives, hazmat)

The bigger the molecule, the more vib. modes:
– Monitoring progress of reactions
– 3N − 5 for linear molecules (e.g. CO2)
– 3N − 6 for nonlinear molecules (e.g. H2O) .
– Where N = number of atoms in molecule 7 5 0 0
MDMA

Intensity (arb. units)

– Diatomics (1 mode)
5 0 0 0

– Proteins…10’s of thousands Cocaine

Vibrations excited by absorption of EM radiation of 2 5 0 0 Heroin
correct energy.
0
5 0 0 6 0 0 7 0 0 8 0 0 9 0 0 1 0 0 0 1 1 0 0
-1
R a m a n s h if t , c m

69 70

Selection Rules Gross selection rule: IR-Absorption

These are very important in vibrational spectroscopy.
The dipole moment, p, of the molecule must change

Used to predict which vibrations you should observe. during the vibration for it to IR active

Rules are different for IR-Absorption and Raman
scattering. • Does not have to have a

Sometimes we see bands in IR and not in Raman …..and permanent dipole…can
visa-versa. move

Raman good for non-polar molecules.
• Some vibrations cause no

IR good for polar molecules.
change in dipole moment
(homonuclear diatomics)
Transitions are restricted to single-quantum jumps to
neighboring levels……e.g. from v=0 to v=1, from v=1 to v=2,
etc
71 72

18
 Changing dipole moment Typical IR spectrum
Plot of
– Original molecule AB: %Transmittance
r
A B Versus
2 atoms + “bond” Wavenumber
⇒ electron cloud
Vibration type V/cm−1

C–H 2850−2960
– Draw bond dipole r
+q -q C–H 1340−1465

– Distort molecule C–C stretch, bend 700−1250

→
p C=C stretch 1620−1680

– Draw new bond dipole C≡C stretch 2100−2260

O–H stretch 3590−3650

– Has dipole changed? C=O stretch 1640−1780

r C≡N stretch 2215−2275
+q -q
N–H stretch 3200−3500
→ Hydrogen bonds 3200−3570
p

3Y-Spectroscopy-NUIG-2008/9 73 74

Environmental Influences (I) Analysis of vibrational spectra (I)

Covalent diatomic molecule HCl:
– Gas-phase (2,886 cm-1),Solid state (2,720 cm-1).
– Aromatic solvent (2,712 cm-1 ), ether solvent (2,393 cm-1).

Conclusion?
– weak intermolecular bonding R2O....H-Cl

Vibrational bands are usually broader in condensed
media (solid liquid) than gas phase.

Crystalline materials have sharper vibrational bands
than amorphous materials:
– Can be used to distinguish polymorphs of pharmaceutical
products.
– Degree of crystallinity in polymers & semi-conductors.

Functional group region most important for interpreting
IR spectra:
– In IR it is the polar covalent bonds than are IR "active".
– In Raman spectra non-polar bonds are also "active".
– In organic molecules these polar covalent bonds represent the
functional groups.

Hence, the most useful information obtained from an IR
spectrum is what functional groups are present within the
molecule.

3Y-Spectroscopy-NUIG-2008/9 75 76

19
 Band areas Analysis of vibrational spectra (II)
Functional group region Fingerprint region
Some functional groups are combinations of different
bond types:

C-H
– Esters (CO2R) contain both C=O and C-O bonds.
– Both are typically seen in an IR spectrum of an ester.
O-H

In the fingerprint region, spectra tend to be more complex
and much harder to assign.
– But very important in Physics, Materials Science,
etc………….properties of materials

Single bonds to
H Phenol…
77 78

Applications of IR spectroscopy (I) Applications of IR spectroscopy (II)

IR spectra of polyatomics are complex:
Can be implemented in microscopes for micron scale

More than just stretching vibrations: analysis.
– Bending, wagging, twisting.
Drawbacks:
– Combinations of vibrations.
Very sensitive to water and other polar molecules

Very good therefore for: – Makes measurements in solution very difficult
– Identification (forensics).
An absorption effect….limits sensitivity & hinders
– Molecular Comparison. sampling.
– Non-destructive testing.
Works in the IR region ⇒ limits optical resolution.
– Seeing changes in molecular environment.

Not very good for quantitative analysis.

79 80

20
 Diatomic Model Modelling vibrations

Both atoms move in a m1 m2
Close to Re the MPE

vibration….. curve….approximates to a

Spring model k parabola (y=x2).

Use Schrödinger wave
Potential Energy (V) can be
equation (see lecture notes): written: V = ½ k(R-Re)2

k = force constant (Nm-1)
h k
Eυ = (v +½) (J ), v= 0, 1, 2, 3,......
2π µ
µ = effective mass (kg), k = force constant (Nm-1 )
v = vibrational quantum number

81 82

Molecular Potential Energy Diagram Vibrational energy levels

Differences?
MPE diagram  Constant
For 2 different 3 (7/2)(h/2ππ)√√ (k/µµ)  ∆E = (h/2π)√(k/µ)
diatomics….  For photon
2 (5/2)(h/2ππ)√√ (k/µµ)
Strong bond E ∆E = hv = hcν
Weak bond

1 (3/2)(h/2ππ)√√ (k/µµ) Therefore

Plot of energy versus internuclear distance: 1 k

0 (1/2)(h/2ππ)√√ (k/µµ)
Minimum = equilibrium bond distance (Re) ν=
0 = dissociation, atoms far apart. 0 2π c µ

83 3Y-Spectroscopy-NUIG-2008/9 84

21
 Calculating the wavenumber of a vibration Wavenumber calculations:
The wavenumber of a vibration can be calculated from the equation:

An 1H35Cl molecule has a force constant of 516 Nm−1. Calculate the
vibrational stretching frequency: 1 k
ν = , where ν is the vibrational wavenumber in m-1 .
The wavenumber of a vibration can be calculated from the equation: 2π c µ
Step 2: input the values:
1 k
ν = , where ν is the vibrational wavenumber in m-1 .
2π c µ 1 (516 Nm -1 )
ν = , [N = kgms -2 ]
mH mCl 2π 2.997x10 ms 1.63 x 10 kg
8 -1 -27

Step 1: Calculate the effective mass, µ = ,

mH + mCl 1 (516 kgms -2 m -1 )
ν = ,
µ=
( 0.0010079 )( 0.03545) × 1 in kg, N a = avogadros number
1.88x109 ms-1 1.63 x 10-27 kg
( 0.0010079 + 0.03545) N a ν =
1
3.165x 1029s -2 ,
µ = 1.63 x 10 -27
kg [Always write this out longhand ] 1.88x109 ms-1
ν = 299, 246 m-1 = 2992 cm -1

85 86

Diatomic Molecules: Anharmonicity (I)

V/cm−1 Re/pm k/(N m−1) D/(kJ mol−1)
Parabolic/spring model does not
1
H 2+ 2333 106 160 256 work at all extensions.
1
H2 4401 74 575 432
2

Untrue for real molecules since
H2 3118 74 577 440 parabolic potential does not allow
1
H19F 4138 92 955 564 for bond breaking.
1
H35Cl 2991 127 516 428
1

MPE curve more complex
H81Br 2649 141 412 363
1
H127I 2308 161 314 295
14
N2 2355 110 2294 942
Actual motion is anharmonic
16
O2 1580 121 1177 494
19
F2 892 142 445 154
35
Cl2 560 199 323 239

1 k
ν =
2π c µ87 88

22
 Convergence of energy levels Morse Potential Energy Curve (II)

Use a function that resembles the Morse Potential Energy
general shape of a molecular  µω 2 
{ } k
2
potential energy curve. V = hcDe 1 − e− a( R− Re ) , a =  , ω =
 2hcDe  µ

Morse Potential Energy Curve
1

Corresponding Schrödinger equation Rem: V= kx 2 where, x = ( R − Re ) for simple HO.
can be solved: 2
– Values of the energies obtained.
– Number of bound levels is finite.
De = depth of the potential minimum.
– Tends to a limit at the dissociation
energy. Near the well minimum the variation of
V with displacement ≈ a parabola.
But allows for dissociation at large
displacements.

89 90

Morse Potential Energy Curve (III) Spring model vs. Morse

Solving the Schrödinger equation for the Morse potential gives
Energy levels unequally 6 6

permitted energy levels (in vibrational wavenumber terms): spaced, converging at high 5 5
energy.
4 4

Amount of distortion
2
ν E
 1  1 2
a increases with increasing 3 3
G (v) =  v + ν −  v +  xeν , xe = =
 2  2 2 µω 4 De energy. 2 2

All transitions are no

ω = k/µ 1 1

longer the same. 0 0

1 k 0
ν = = vibrational wavenumber.
2π c µ
nd
2 term in the expression subtracts from the first with increasing effect
G(υ ) =(υ +½)hcν,...........................simple spring model
as v increases, and hence gives rise to the convergence of the levels
at high quantum numbers. G(υ ) =(υ +½)hcν − (υ +½) 2 hcν xe ....Morse model

91 92

23
 Overtones & Hot Bands Example:

Anharmonicity results in allowed transitions for: HCl has a fundamental band at 2,885.9 cm −1 ,

Transitions of ∆v > 1 are allowed: and an overtone at 5,668.1 cm −1.

– Fundamental (0→1). Calculate we and the anharmonicity constant xe .

– Overtones (0 → 2): Step 1: Equation: G(v) = (v + 1/2)νe - (v + 1/2) 2νe xe .

Enables calculation of Anharmonicity constant xe. For the overtone band, v=2 ⇒ E 2 = (2 + 1/2)νe − (2 + 1/2) 2νe xe
– Basis of NIR spectroscopy (overtones of OH, CH, NH). For the fundamental band, v=1 ⇒ E1 = (1.5)νe − (1.5) 2νe xe

For anharmonic oscillator, all values of ∆v are allowed: For zero point energy, v=0 ⇒ E 0 = (0.5)νe − (0.5) 2νe xe
– ∆v > 1 transitions, only weakly allowed if anharmonicity is Step 2: Input values & solve:
slight. 2885.9 cm −1 = E1 − E 0 = νe − 2νe xe
νe = 2989.6 cm −1
– Hot bands (1 → 2) 5668.1 cm −1 = E 2 − E 0 = 2νe − 6νe xe
⇒ xe = 0.0174

93 94

3rd year quantum: 4th Topic Background

Vibrational-Rotational Spectroscopy :
In condensed phases (liquid, solids) the lower energy
– High resolution spectroscopy. transitions are all hidden in the gross vibrational
– Selection Rules. spectra….
– P-Q-R branches.

In the gas phase, where there is little intermolecular
– Combination Differences.
interactions:
– Calculating energies of transitions.
– Use a high resolution spectrometer:
– Can Resolve the vibrational bands into many individual

Understand and be able to explain high resolution
narrower bands…..~10 cm-1 separation
vibrational spectroscopy and the selection rules. Be able
to calculate energy levels and rotational constants. – ⇒ rotational modes
– Sec.19.14: Elements of Physical Chemistry, 4thed., p.502 (intro).
– Sec. 13.12, Physical Chemistry, Atkins 8th ed., p.457.

95 96

24
 High resolution spectrum of HCl High resolution infrared (Energies)
Combining Vibrational + rotational energy changes:
1 h k
Eν = (ν + )
2 2π µ
In terms of joules (J) ⇒
 h2 
E J = J(J+1)  2 
 8π I 
Energy of a rotational-vibrational transition is:
1 h k  h2 
Eν , J = (ν + ) + J(J+1)  2  , or
2 2π µ  8π I 

The lines appear in pairs because H35Cl and H37Cl both
contribute (their abundance ratio is 3:1). 1 h k h2
– Mode is H-Cl stretch Eν , J = (ν + )ωe + Bv J ( J + 1) Where ωe = Bv =
2 2π µ 8π 2 I

97 98

High Res. IR (Selection rules) Q branch selection rule

E(v,J) = (v + 1/2)ħ(k/µ)1/2 + J(J + 1)Bv

Selection rule: ∆v= +1, ∆J = ±1 (& sometimes 0)
– Rotational energy change must accompany a vibrational energy
change.

On low energy side, ∆J = –1, = P Branch.
– Intensities mirror populations of starting levels

On high energy side, ∆J = +1, = R branch.

For ∆J = 0, Q branch

Q branch ∆J = 0,

Is allowed only when there is angular momentum around
the axis of a linear molecule
– e.g. NO has Q branch because of single π electron

For spectrum of HCl there is a gap at the expected
location of the Q branch because it is forbidden.

For CO2…some modes do/others don’t:
– Asymmetric stretch…no Q branch
– Bending mode…has an Q branch

99 100

25
 Vib-Rot transitions Combination Differences (I)

Separation between lines on P J'=3
Anharmonicity of the vibration results in a slightly
& R branches is 2B VIBRATIONAL extended bond in the upper state.⇒
J'=2 EXCITED STATE

Can determine bond lengths – Rotational constant of the vibrationally excited state, B1 is
– Without needing pure MCWE J'=1
v=1, J'=0 usually smaller than that of the ground vibrational state, B0,
spectrum.
– Easier experimentally
As a result, the Q branch (if it exists) consists of a series
– But MCWE is more precise of closely spaced lines.

R branch lines converge slightly as J increases.
J=3

P branch lines diverge slightly as J increases.
VIBRATIONAL
J=2
GROUND STATE
J=1
v=0, J=0

101 102

Combination Differences (II) Combination Differences (III)

Transitions νR ( J − 1) & νP ( J + 1)
νP ( J ) = ν − ( B1 + B0 ) J + ( B1 − B0 ) J 2
have a common upper state (B1 , J):
νQ ( J ) = ν + ( B1 − B0 ) J ( J + 1) ⇒ Energies/ν Depend only on B0 .,
νR ( J ) = ν + ( B1 + B 0 )( J + 1) + ( B1 − B0 )( J + 1) 2 Differences in ground state energies,

 h -1 
1
 νR ( J − 1) − νP ( J + 1) = 4 B0 ( J + )
 Remember B = 8π 2 cI for cm  2
To measure B1 and B0 , use method of combination differences. νR ( J ) &νP ( J ) have a common lower state (B0 , J):
Set up expressions for the difference in the wavenumbers Differences in upper state energies,
of transitions to a common state ⇒ resulting expression: and so from previous:

depends solely on properties of the other state. 1

νR ( J ) − νP ( J ) = 4 B1 ( J + )
2

103 104

26
 Combination Differences (IV)

Plot of the combination difference against J + ½ should
be a straight line of slope 4B0 or 4B1,⇒
– Rotational constant of the molecule in the state v = 0 or V=1 can
be determined [see practical no. 3.5]
– B1 should be less than B0
– If slope not linear ⇒ Centrifugal distortion at play
– Remember to check units (cm-1 or J)
105
Example: HBr….part 2:
Step 2: Equations & Input values:
For Transitions with a common upper state (v=1, J=1):
1
νR ( J − 1) − νP ( J + 1) = 4 B0 ( J + )
2 –
⇒ 2575.19 (cm -1 ) - 2525.25 (cm -1 ) = 4B0 (1+1/2) = 6B0
B0 = 8.35 cm -1
For Transitions with a common lower state (B0 , J):
1 – Sec. 19.12 & 19.15: Elements of Physical Chemistry, 4th ed.
νR ( J ) − νP ( J ) = 4 B1 ( J + )
2 – Sec. 13.13 & 13.16: Physical Chemistry, 8th ed. Atkins.
⇒ 2590.95 (cm -1 ) - 2542.25 (cm -1 ) = 6B1 ⇒ B1 = 8.12 cm-1
107
Example: HBr….part 1:
The Vibrational-Rotational spectrum of HBr has many absorption
lines, four of which are at: 2590.95, 2575.19, 2542.25, and 2525.09 cm -1.
What is the fundamantal vibration and the rotational constants for the
ground and first vibrationally excited state?
Step 1: Analysis of data & assignment of transitions:
Seperation is ~ 15 cm -1 except between 2nd & 3rd where it is double this.
⇒ Missing transition lies around 2560 cm-1.
⇒ 2575 is (v=0, J=0) → (v=1, J=1) transition (R branch)
⇒ 2590 is (v=0,J=1) → (v=1,J=2) transition (R branch)
⇒ 2542 is (v=0,J=1) → (v=1,J=0) transition (P branch)
⇒ 2525 is (v=0,J=2) → (v=1,J=1) transition (P branch)
106
3rd year quantum: 5th Topic

Raman Spectroscopy:
– Overview and Instrumentation.
– Selection rules & their consequences.
– Rotational Raman.
Comparison between MIR and Raman.
– Raman Microscopy

Understand and be able to explain Raman spectroscopy
and the selection rules. Describe the instrumentation and
the pros/cons of the method.
108
27
 Scattering process 2 Types of scattering

99.999 %+ of the incident light is Rayleigh scattered:

Scattering of monochromatic light by materials:
– Molecules of a gas, liquid or solid
– Usually NIR, Visible, or UV light used

Light does not have to pass through sample:
– Can analyze lots of different material types
– No change in wavelength of incident light.
– Elastic scattering from molecules & materials

<0.001% of the light is Raman scattered:
– either greater than original or less than original by a constant amount
determined by molecular energy levels
– independent of incident light frequency

109 110

Raman scattering (I) Raman Scattering (II)

Rayleigh scattering:

Light interacts with the vibrational modes of molecules
– 103 – 104 weaker than incident light.
& materials.

Raman scattering:

Bands at Longer & Shorter wavelengths. – 103 – 105 weaker than Rayleigh.
RAYLEIGH
Ratio between Stokes & Anti-
Stokes:
– Populations of E levels.
Stokes shift…to – Boltzmann Distribution.
longer wavelength – Dependant on temperature:
RAMAN
(STOKES) RAMAN
(ANTI-STOKES)
Anti-Stokes to
shorter
wavelength. (υ0−υ1) υ0 (υ0 +υ1)
Frequency, cm-1 nJ ∝gJ exp(−εJ / kT)
111 112

28
 Raman Scattering (III) Raman spectrometer: schematic
R a y le ig h s c a tte rin g , 0 c m -1 (re la tiv e ),

e x. = 5 3 2 n m = 1 8 7 9 6 c m -1 a b s o lu te

R a m a n s c a tte rin g : R a m a n s c a tte rin g :

Intensity

S to k e s : 0 -4 0 0 0 c m -1 (re l.) a n ti-S to k e s : 0 -4 0 0 0 c m -1 (re l.).

5 3 2 -6 7 6 n m (a b s ). 4 3 9 -5 3 2 n m (a b s .).

0 -4 0 0 0 c m -1 E n e rg y , c m -1

IR a b s o rp tio n

Scattered light relative to the excitation line Can replace the focussing lens/microscope with a fibre optic pro

Can use any wavelength excitation

113 http://www.andor.com/chemistry/?app=64
114

Raman spectrometers: Typical Raman Spectra

4000

3500
Pure Cocaine taken using
3000
a Battery operated
2500
portable system
2000

1500

1000
A11AUG13:11/8/97.

30000
500 Cocaine hydrochloride,
Portable 0
pure.

200 400 600 800 1000 1200 1400 1600 1800

Microscopy:

INTENSITY (arb.)
20000

Pure Cocaine taken using

10000
a Laboratory system
High Throughput
300 500 700 900 1100 1300 1500 1700
-1
Raman shift, cm .

115 116

29
 Light sources: Detectors & Filters:

Light sources: nearly always Lasers
Filter out excess Rayleigh scattered excitation light using:
– Monochromatic, Highly directional, Intense. – Holographic or edge filters.
– Narrow, stable linewidths needed.
– In days used a monochromator
– In olden days…sunlight, lamps used.

Light is detected using a CCD detector:

Most Common sources:
– 785 & 830 nm laser diodes (near-IR). – Usually cooled for max. sensitivity / lowest noise.
– 633 nm He-Ne. – 1024 or 2048 pixels in detector.
– 532 nm Diode pumped lasers. – Whole spectrum in one shot (fast < 1 second. scan).
– 514 & 488 nm lines from Argon Ion. – In olden days they used PMT’s & photographic film.
– 244 nm frequency doubled Argon Ion.

117 118

Raman spectrum of CCl4 Selection Rules: Raman

Gross selection rule for vibrational Raman transitions: -
the polarizability should change as the molecule vibrates.

As homonuclear and heteronuclear diatomic molecules
swell and contract during a vibration:
– The control of the nuclei over the electrons varies,
– Hence the molecular polarizability changes:
– Both are therefore vibrationally Raman active.

Spectrum highly symmetrical:

Peaks at ± 218, ± 314 and ± 459 cm-1
– shifted from the original incident radiation at 633 nm (15,800 cm-1).

119 120

30
 Gross selection rule: Raman spectroscopy Specific Selection Rules: Raman

Has to be a change in the polarizability for a vibration to be
Anti-Stokes lines: lines to high frequency of the incident
Raman active: radiation: ∆v = −1.
CO2 symmetric Stretch
Stokes lines: lines to low frequency: ∆v = +1.

The intensities of the anti-Stokes and Stokes lines are
O C O O C O O C O
governed largely by the Boltzmann populations of the
vibrational states involved in the transition.
– anti-Stokes lines are usually weak because very few molecules
are in an excited vibrational state initially.
Distortion of the electron cloud of a molecular entity
by a vibration.
Good for Homonuclear diatomics (N2, O2 etc.)

121 122

Exclusion Rule: Selection Rule: CO2 example

More exact treatment of IR and Raman activity

of normal modes leads to the exclusion rule:

If a molecule has a centre of symmetry (like

CO2), then no modes can be both infrared and
Raman active:
– A mode may be inactive in both.

Symmetric stretching vibration of CO2
– often possible to judge intuitively if a mode changes the
molecular dipole moment,
Polarisability changes
– use this rule to identify modes that are not Raman active – therefore Raman band at 1,340 cm-1

Dipole moment does not
– no absorption at 1,340 cm-1 in IR

123 124

31
 Selection Rule: CO2 example Rotational Raman spectroscopy (I)

Molecules must be
Anisotropically polarizable:
– Non-isotropic polarisability (i.e.
molecule must not be spherically
symmetric like CH4, SF6, etc.)
– Polarizability may be different when

Asymmetric stretching vibration of CO2 the field is applied (a) parallel or (b)

Polarisability does not change during vibration: perpendicular to the molecular axis:
– No Raman band near 2,350 cm-1

Dipole moment does change:
– CO2 absorbs at 2,349 cm-1 in the IR (very strong)

125 126

Rotational Raman spectroscopy (II) Rotational Raman (II)

Distortion induced in a molecule by
All linear molecules and diatomics (whether homonuclear or
an applied electric field returns to its heteronuclear) have anisotropic polarizabilities:
– ⇒ are rotationally Raman active.
initial value after a rotation of only

Rotational Raman spectroscopy can be used to study many of the
180 °
molecules that are inaccessible to microwave spectroscopy:
– twice a revolution. – E.g. N2. O2….etc..

Therefore for Rotational energy
Spherical rotors such as CH4 and SF6, however, are rotationally
levels in Raman: Raman inactive as well as microwave inactive
– ∆J = ± 2 – This inactivity does not mean that such molecules are never found in
rotationally excited states.
– Molecular collisions do not have to obey such restrictive selection rules, and
hence collisions between molecules can result in the population of any
rotational state.

127 128

32
 Rotational Raman (I)

The rotational energy levels of
a linear rotor and the
transitions allowed by the ∆J =
± 2 Raman selection rules.

Relative intensities determined
by Boltzmann distribution:
Example: CO2 Pure Rotational Raman

CO2 rotation is Raman active:
– ~ 20 absorption lines are visible on
either side of the Rayleigh scattering
peak
– Max.intensity for J=7 → J=9.
– The ∆J = +2 and ∆J = -2 are nearly
equal in intensity

Very near high intensity peak of
exciting radiation.

( −εJ / kT)
Very high resolution

nJ ∝ gJ e spectrometers:
– Filter out Rayleigh light.

129 130

Vibrational Raman Spectroscopy Raman of Cocaine.HCl & crack cocaine

Is it Heroin? Is it Cocaine? Is it MDMA?
Raman can
discriminate cocaine
7500 MDMA and free base in <5
seconds.
Intensity (arb. units)

Forensics lab method

5000
takes ~several
Cocaine hours…..
Heroin
2500

0
500 600 700 800 900 1000 1100
-1
Ram an shift, cm

131 132

33
 Advantages of Raman spectroscopy Drawbacks of Raman spectroscopy

Light does not have to pass through sample:
Inherently very weak:
– Allows facile analysis of wide variety of materials. – Billion of photons in…..maybe one back with information.
– NO SAMPLE PREPARATION.

Coloured samples can absorb laser light & burn:

Spectra are unique so can be used to ID materials – Particularly bad for FT-Raman, λex = 1064 nm.
conclusively (high specificity).

Fluorescence of sample can obscure Raman data:

Non-destructive analysis on the nm to nm scale.
– Many materials are naturally fluorescent.

Can analyse aqueous solutions easily.
– Fluorescence more efficient than Raman.

Operates in UV-VIS-NIR region of EM spectrum:
– Simple optics, fibre probes, microscopy, etc.

Instrumentation more expensive than FT-IR.

Fast….analyses in ~1 second or less are possible.

133 134

Raman vs. IR spectroscopy Raman vs IR; case 1 --- CHCl3

How do the 2 different vibrational techniques compare?
Which is which?

How do the selection rules work in practice for – Go back to fundamentals.
polyatomic molecules?
Very similar:
– Changes in polarizability vs. dipole? – Why?

What are the advantages/disadvantages?
Differences?
– Which samples work best? – Selection rules…

How can we use the techniques for advanced studies?

135 136

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 O O
Ethanol (C2H5OH) 2,4-Pentanedione
C C
H3C C CH3
H2
O-H O-H Scales not exact match IR-Absorption Raman
stretch bend
Polar groups give Strong
strong C-H
IR bands….weaker in
Raman Weak Weak
C-H C=O
Different selection
rules
Weak O-H bands
mean can use OH Strong
containing solvents C=O

Data from: ww.aist.go.jp/RIODB/SDBS 137 Data from: ww.aist.go.jp/RIODB/SDBS 138

Octane: CH3-(CH2)6-CH3 Spectral Ranges

IR is usually limited to the window materials used:
Raman
– KBr, CsI, NaCl.
– Can’t measure very weak vibrations (<400-600 cm-1).

Raman mainly operates in visible EM region:

– Optics transparent in 0 - 4000 cm-1 range
– Use good optical filters…
– Can measure down to ~ 5 cm-1.
– Materials characterisation
C-H stretch

Cataliotti et al. Phys. Chem. Chem. Phys. 4, 2774-2779, (2002).

Data from: ww.aist.go.jp/RIODB/SDBS 139 140

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 IR versus Raman: comparison Applications in Microscopy
IR-absorption Raman
Can use IR and Raman in microscopy:

IR radiation = long wavelength = large spot size:
Selection rule Change in Dipole moment Change in polarizability
– In practice spot ~10 µm
Good for Polar molecules (e.g. HCl) Non-polar molecules (e.g. N2)

UV-Vis = shorter wavelength = smaller spot size:
Water Very strong absorption Very weak scattering
– For 488 nm excitation, spot < 1 µm
Wavelength IR region of spectrum Any region

Water is a weak Raman scatterer:
Normal Spectral Typically (600-4000 cm-1) Better (200-4000 cm-1) – Can use Raman for analysis of cells & tissue.
range – Can do aqueous vibrational spectroscopy.
Sensitivity Good Very weak

141 142

Raman microscopy (I) Raman microscopy (II)-explosives

Rayleigh-line 2900 cm-1 Stokes-shift: Stokes-shift of :

(0 cm-1): CH2 stretching 3400 cm-1 Raman mapped image for two
shows modes:
the diffraction at
broad water band explosives:
the oil droplets and
the edges of the oil surrounding water Red RDX. Green PETN
droplets.

143 J. Phys. Chem. B, Vol. 108, No. 26, 2004 8801 144

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