Part II

Molecular Spectroscopy
Prof. Dr. Xin Lu (吕鑫)
Office: 曾成奎楼 B301、卢嘉锡楼234
Email: xinlu@xmu.edu.cn
http://pcoss.xmu.edu.cn/xlv/index.html
http://pcoss.xmu.edu.cn/xlv/courses/theochem/index.html
 Recommended books
• Fundamentals of Molecular Spectroscopy, C. N. Banwell and E. M. McCash,
4th Edition, McGraw Hill
A good introductory level
• Physical Chemistry, Donald A McQuarrie and John D. Simon
University Science Books
Good for other parts of the course too

Jmol-1 calmol1 eV cm-1

1 Jmol-1 1 0.2390 1.03610-5 8.35910-2
1 calmol-1 4.184 1 4.33610-5 0.3497
1 eV 9.649  104 2.306  104 1 8.065  103
1 cm-1 1.196  10 2.859 1.24010-4 1
 The Electromagnetic Spectrum
• To convert frequency in rad
s-1 to wavenumbers divide
by 2𝒄 (𝑐 ~ the speed of 无线电 微波 红外 可见 紫外 X射线 射线
light in cms-1)
𝑐 = 2.9979251010cms-1

Wave length
Wavenumber
 = c/ Freq. in Hz
E = hc/ Energy

• To convert wavenumbers to
energy in joules, multiply by
h𝒄 (1 eV ≡ 8065.5 cm-1).
 1. Introduction

Spectroscopy may be defined as the interaction of electromagnetic radiation with matter.

 NMR and IR (learnt) : qualitative tools to determine the structure of molecules.

 In this part, we shall study:

i) the more fundamental principles of spectroscopy using the ideas of Quantum Mechanics.
(Spectroscopy provides some of the best experimental evidence for many of the ideas of
quantum mechanics!)
ii) how to determine fundamental parameters such as bond lengths and energy levels by analyzing
the fine structure of spectra.
 Quantization of energy :
 In QM, the energy that a molecule possesses is quantized.
 When a molecule is excited from one energy level to higher one, electromagnetic radiation
(light) is absorbed.
 When a molecule relaxes from a higher energy level to a lower one, light is given out.
These processes give rise to absorption and emission spectra, respectively.

Absorption: Spontaneous emission:

M + h  M* M*  M + h
E Excited molecule

h h
 Stimulated emission
• The emission of a photon may either be spontaneous, as above, or it could be
stimulated by another photon.
• In this process a photon of the correct energy stimulates the molecule to return to a
lower energy level with the emission of a photon of the same energy.

Stimulated emission

M* + h  M + 2h

The most important application of stimulated

h 2h emission is laser (Light Amplification by
Stimulated Emission of Radiation)!
 Contributions to the total energy of a molecule
Consider the molecules in the gas phase:
• Constantly moving around (translational energy), rotating, and vibrating.
• Given enough energy, their electrons could be excited to higher energy levels.
• All of these energies are quantized.
• But we can disregard translational energy levels i) because they are so close in energy and
ii) because light does not cause a transition between translational energy levels.
• We can assume that these energies are independent of one another:
Etotal = Eelectronic + Evibrational + Erotational (Born-Oppenheimer Approximation)
• Similarly, when a molecule is promoted from one energy level to another, we can
approximate the change in energy as,
Etotal = Eelectronic + Evibrational + Erotational
with Eelectronic >> Evibrational >> Erotational
 Energy (cm1) The different energy levels for carbon monoxide

1st electronic
excited state

Electronic
ground state

• Each electronic state has many vibrational energy levels associated with it.
• Each vibrational state has many rotational energy levels.
 Since the energies required for the different types of transition vary
considerably, they correspond to absorptions or emissions in different
parts of the electromagnetic spectrum.
• Eelectronic typically 10,000s cm1 Visible/UV, possible x-ray for core e
• Evibrational typically 1,000s cm1 Infra-red (IR)
• Erotational typically a few cm1 Microwave/radiowave

 A IR photon that causes a vibrational transition can also cause a concomitant

rotational transition. Spectral phenomena?

 Almost all molecules when they are vibrationally excited are also simultaneously
rotationally excited.
 The same is true for electronic transitions -- each is usually accompanied by a
simultaneous vibrational and rotational transition. Spectral phenomena?
 Iodine vapor, violet due to absorbing light in the yellow-green part.
I2 + hv (~540 nm)  I2* (see its UV-vis spectrum given below!)
Each of these peaks corresponds to the same electronic transition but with a different
change in the vibrational (and indeed, rotational) energy of the iodine molecule.

Excitations from vibrational ground state

Excitations from vibrational 1st excited state

Excitations from vibrational 2nd excited state

(see next page for details)

The ultrafine structure of UV-vis Spectrum

• Transitions from the • Transitions from the 1st • Transitions from the 2nd
vibrational ground state. vibrational excited state. vibrational excited state.
2. Vibrational Spectroscopy - the Harmonic Oscillator(HO)
双原子分子振动的谐振子模型
Potential energy curve of a
diatomic molecule
• Restoring force acting on the molecule : –dV/dr
• At the equilibrium separation re, –dV/dr = 0

re • The simplest assumption:

restoring force  –(r–re) = –kx (let x = r–re)
k = force constant (in N m-1),
larger k, harder it is to stretch/compress the bond.

• The potential energy can thus be given by:

V(x)= –∫–kxdx = kx2/2 + constant
constant=0, so V(0) = 0; Ex.1
• A good approximation for small displacements from re.
 Classical harmonic oscillator
 For a classic harmonic oscillator, e.g., a weight of mass m on a spring.
• The frequency of oscillation is constant, but the amplitude varies.
• At larger amplitudes, the energy of the system is greater, i.e., greater stretch,
greater potential energy, but the frequency of oscillation remains the same.
• This intrinsic frequency of oscillation, given the symbol , is given by:
Mass-spring
= 𝒌/𝒎 (in rad s-1) --角频率（弧度/秒）
 For a system comprised of two vibrating masses, m1 and m2, the frequency depends
on their reduced mass, .
= 𝒌/ (in rad s-1) with  = m1m2/(m1+m2)

 To convert to Hz, the frequency in rad s–1 is divided by 2:

 (in Hz) =  (in rad s–1)/2 = (2)–1 𝒌/

• In vibrational and rotational spectroscopy, wavenumbers are often used as a
measure of frequency (the wavenumber representing the number of waves in one
centimeter).

 = wavenumber in cm–1 = 1/ ( in cm) non-standard symbol of freq.

𝝎 (in cm–1) = (2𝑐)–1 𝒌/

(𝑐 non-standard symbol for the speed of light in cm s–1)

 = c/

 (in Hz) = 𝒄/ ( in cm) = 𝒄

 QM Treatment for Harmonic Oscillator
• Vibrational energies are quantized and found by solving the Schrö
dinger equation for
the harmonic oscillator:
ћ𝟐 𝒅𝟐 𝟏 𝟐
− 𝟐
+ 𝒌𝒙  = 𝑬
𝟐 𝒅 𝒙 𝟐
Kinetic energy (Ek) associated Potential energy (V) associated with the
with the wavefunction. wavefunction.
 There are infinite number of solutions, v, with corresponding energy Ev:

Ev (in Joules) = (v + ½)ћ (v ~ vibrational quantum number, 0,1,2,3…)

( in rad s-1)
or v (in cm-1) = (v + ½)𝝎 (𝝎 in cm-1)
 Quantized energies of harmonic oscillator
• The energies of the first seven wavefunctions of the harmonic oscillator are shown
below together with the potential energy function. v = (v + ½)𝝎
VHO = kx2/2 Total Energy • For each quantum state of the HO,
v
13𝝎/2 , V=Vv,max = v
i) At x = xv,max or xv,min, Ek = 0？
11𝝎/2 ii) At x = 0 , V = 0, Ek= Ek,v,max = v
9𝝎/2
7𝝎/2 • The lowest energy ε0 = 𝝎/2 is known as the zero-
𝝎 point energy, i.e., a bond is always vibrating, even
5𝝎/2
𝝎 in its lowest energy state.
3𝝎/2
𝝎 • Selection rule for transitions: v = +/-1
𝝎/2
x0,min 0 x0,max • What does the vibrational absorption spectrum
In each state, oscillating look like?
between these extremes.
Ex.3,4
 The Morse Oscillator
• The harmonic oscillator description is problematic for larger displacements of a bond.
• A much better description of an oscillator can be gained using the empirical Morse
potential (VM) that agrees much better with experiment.
VM(x) = De[1  exp (βx)]2 (x = r–re; De – Depth of the well;  – steepness of the well)
must be dimensionless! units of reciprocal length
The Morse potential of H2
De = 440 kJ mol-1 • For small displacements (x << 1/),
re = 0.741 Å
 = 1.93 Å-1 '= 2 ex ≈ 1 x (e = 1  + /2!/3! …)
(BDE ~ 436 kJ mol-1) Harder to stretch the bond
but the same BDE!  VM(x) ≈ Deβ2x2 = kx2/2
(with k = 2Deβ2)
i.e., the oscillator becomes harmonic.
 QM Description of the Morse Oscillator
• The Schrö
dinger equation for the Morse Oscillator,
ћ𝟐 𝒅𝟐
− + 𝑽𝑴  = 𝑬
𝟐 𝒅𝟐𝒙
 Ev (in joules)= (v + ½)ћω – (v + ½)2ћωxe
ħ𝜷𝟐
xe = (anharmonicity constant)
𝟐𝝁𝝎
or v (in cm-1)= (v + ½) 𝝎 – (v + ½)2𝝎xe

 From  (and ), kM can be calculated. kM == 2 Note:  = 2𝑐 𝜔 in rads1

 Then from xe,  and De can be calculated.  = 2𝜇𝜔𝑥𝑒 /ħ

 Effects of xe (anharmonicity constant) Typically 0 < xe < 0.1.

Morse oscillator Harmonic oscillator

EvM = (v + ½)ћω – (v + ½)2ћωxe EvHO = (v + ½)ћω
EvM = EvM  Ev-1M = ћω  2ћωxe EvHO= EvHO  Ev-1HO = ћω
H.O.

M.O.
i) EvM always < EvHO

ii) EvM always < EvHO

iii) EvM gets smaller with increasing v,

eventually approaching 0. That is, Ev
reaches its maximum.
Ex.2
 Maximum of Ev(v) v (in cm-1)= (v + ½)𝝎 – (v + ½)2𝝎xe
vM = vM  v-1M = ћ𝝎  2ћ𝝎xe v , vM; vM  0, vMmax = De!
• Eventually the 𝜺𝑴
 reaches a maximum at vmax and then falls.
𝑴 These points have no
• This 𝜺 𝒎𝒂𝒙 corresponds to the energy De. physical meaning!
To determine vmax and De, define H2
dv/dv = 0 
d[(v + ½)𝝎 – (v + ½)2𝝎xe]/dv=0
De
 max = (xe1  1)/2
max
 𝑫e = (vmax + ½) 𝝎 – (vmax + ½)2𝝎xe
 𝑫e (in cm-1) = 𝝎(4xe)1
Q: In practice, is the as-derived vmax an integer?
)1
or De (in joules) = ћ(4xe
Dissociation energy De and D0
(BDE: Bond dissociation energy D0) (Depth of well)

𝑫e
𝑫0 = 𝑫e  𝟎

Zero-point energy
0
 Populations of the different energy levels
Populations of the different vibrational energy levels are given by the Boltzmann distribution.
• The probability of an oscillator to occupy the vth level is
𝑷𝒗=𝒆−𝑬𝒗 /𝒌𝑻 / 𝒆−𝑬𝒗 /𝒌𝑻
𝒗
(式中k 为玻尔兹曼常数， 1.380649 × 10-23 J/K ）
• The ratio of Nv, the population of the vth level, to N0, the population of the ground state (v
= 0), is given by:
𝑵𝒗 𝑵𝟎 =𝒆−𝑬/𝒌𝑻 (𝑬 = 𝑬𝒗 − 𝑬𝟎)
• Since E is large relative to kT, only the ground state is significantly populated at room
temperature. (Boltzmann constant k = 1.380649×10−23 J/K = 0.69503476 cm–1/K)
• For example, E1-0 = 2000 cm–1, kT (T=300K) ≈ 200 cm-1

𝑵𝟏 𝑵𝟎 ≈ 𝒆−𝟏𝟎 ≈ 𝟓𝟏𝟎−𝟓
 Transitions in the Anharmonic Oscillator
Selection rule for Harmonic oscillator: v = 1,  =  (a single line in spectrum!)
 Selection rules for anharmonic oscillator: hot bands, e.g,v(21)
• v = 1, 2, 3, … (Less strict!) usually very weak!
• A change in dipole moment during vibration!
Allowed transitions are not equally intense,
depending on the population of the level excited.
v(30) 2nd overtone
The transition from v=0 to v=1, labeled v(1-0) or
v(10), is usually very strong, but transitions to v = 1 usually very
higher vibrational levels rapidly become very weak low population!
in intensity (hardly observable!) v(20) 1st overtone
The transitions that become more important at higher v(10) strong
temperatures are called hot bands. Fundamental
 Frequencies of transitions
v (in cm-1)= (v + ½)𝝎 – (v + ½)2𝝎xe
• v=0 to v=1; v(10) The fundamental absorption! (基频吸收(峰))
 = 1 - 0
= (1 + ½) 𝝎 – (1 + ½)2𝝎xe – [(0 + ½) 𝝎 – (0 + ½)2𝝎xe]
= 𝝎(1 – 2xe) < 𝝎 (基频峰值略小于振子的特征振动频率！)

• v=0 to v=2; v(20) 1st overtone(第一泛频), weak in intensity!

 = 2 - 0
= (2 + ½) 𝝎 – (2 + ½)2𝝎xe – [(0 + ½)𝝎 – (0 + ½)2𝝎xe]
= 2𝝎(1 – 3xe) Just a little less than twice freq. of fundamental!
 Frequencies of transitions
v (in cm-1)= (v + ½) 𝝎 – (v + ½)2𝝎xe
• v=0 to v=3; v(30) ---- 2nd overtone, very weak!
 = 3 - 0
= (3 + ½)𝝎 – (3 + ½)2𝝎xe – [(0 + ½) 𝝎– (0 + ½)2𝝎xe]
= 3𝝎(1 – 4xe)
• v=1 to v=2; v(21) ---- hot band (visible at high temperature!)
 = 2 - 1
= (2 + ½) 𝝎– (2 + ½)2𝝎xe – [(1 + ½) 𝝎– (1 + ½)2𝝎xe]
= 𝝎 (1 – 4xe) ----Almost the same freq. as the fundamental!
 An IR Spectrum of Carbon Monoxide Ex. 5,6

Fundamental 1st overtone

v=0 v=1 v=0 v=2

2143.26 cm-1 4260.04 cm-1
𝝎 – 2𝝎xe 2𝝎– 6𝝎xe

2nd overtone, v=0 v=3

3𝝎– 12𝝎xe

Q1: What do the fine structures in each of the absorption bands mean?
Q2: From the spectrum, how to determine 𝝎 and xe, and hence kM, De, D0 and ?
 Practical way
The easiest way to find these parameters in practice is to take the differences
between successive lines in the spectrum.
e.g., CO
v =(v + ½) 𝝎 (v+1v) –
v – (v + ½) 𝝎xe
2  (v+1v) (v+2v+1) v (10) ~ 2143.26 cm -1

𝝎–2𝝎xe v (20) ~ 4260.04 cm -1

0 𝝎/2 –𝝎xe/4
𝝎–2𝝎xe v (21) ~ 2116.78 cm-1
1 3𝝎/2 –9𝝎xe/4 2𝝎xe
𝝎–4𝝎xe 2𝝎xe= (10) –(21)
2 5𝝎/2 –25𝝎xe/4 𝟐𝝎–6𝝎xe
2𝝎x = 26.48 cm -1
e
𝝎–6𝝎xe 𝝎 = (10)+ 2𝝎xe
3 7𝝎/2 –49𝝎xe/4 𝟑𝝎–12𝝎xe = 2169.74 cm-1
2𝝎xe= 2(10) – (20) xe = 2𝝎xe /(2𝝎) = 0.006102
Q： Can we get such information that is related to bond length from a vibrational spectrum?
 Vibration-rotation spectrum
The fundamental absorption in the IR spectrum of CO is a band of many peaks.
Each peak in this band corresponds to the same vibrational transition from v = 0 to v = 1
but accompanied by a different rotational transition.
This is so-called vibration-rotation spectrum of CO.

 To understand the physical

Fundamental meaning of these fine
v=0  v=1 structures, we need to look at
pure rotational spectroscopy
2143.26 cm-1 first.
𝝎 – 2𝝎xe
 3. Rotational (microwave) spectroscopy
Transitions between rotational energy levels in molecules usually give rise to peaks in
the microwave / radio region of the electromagnetic spectrum.

Rotational angular momentum r  rad s-1

m
The momentum of inertia of the rotating mass (in an angular velocity ) is given by,

I = mr2 Analogous to mass in linear motion.

The rotational angular momentum (L) is given by,

L = I Analogous to p=mv.

The kinetic energy (Ek) associated with the rotating mass is given by,
Ek = I2/2 = L2/(2I) Analogous to Ek = mv2/2 = p2/2m.
 In general for a three-dimensional object, its total angular momentum can be
resolved into its components about the x, y, z axes.
Ltotal = Lx + Ly + Lz
The component rotational angular momenta are given by the equations,
Lx = Ixx, Ly = Iyy, Lz = Izz
Ix ~ the momentum of inertia about the x axis
x~ the component of angular velocity about x axis

 Thus a molecule has three principal moments of inertia, one about each axis.
 For a rotating molecule, the x, y and z axes are chosen by a set of conventions.
For example, the z-axis is chosen to be the highest order of rotational symmetry.
 e.g., SF6
• Moment of inertia about each axis is the same:
Ix = Iy = Iz
• Such a molecule is classified as a ‘spherical top’.

e.g., H-CN

• Linear molecule, bond axis as z-axis!

• Moment of inertia about z axis, Iz, is negligible.
• Ix = Iy
 The rigid rotor model for a rotating molecule
 rad s-1
A simple rotating diatomic molecule may be model by a rigid
m1 r m2
rotor consisting of two masses.
Center of mass
The moment of inertia for such a system is given by: (balance point)
I = r2,  = m1m2/(m1+m2) ~ reduced mass Ex.7
Solving the Schrödinger equation for the rigid rotor gives an expression for the energy it
may possess:
EJ = BJ(J+1), J (rotational quantum number) = 0,1,2,3,…
(Note: E = L2(2I)1 & L2 = ℏ2J(J+1) )
B is the rotational constant for a particular rotor given by:
𝑩 = 𝒉𝒄𝑩 𝒉
B= ћ2/(2I) (joules) 𝑩 (in cm-1) = 𝟐 Ex.9-12
𝟖𝝅 𝒄𝑰
 Energy levels for a rigid rotor
The energy levels for the rigid rotor in wavenumbers are given by:
J = 𝑩J(J+1) J = 0,1,2,3,…
Hence the spacing between adjacent rotational energy levels increases with J.

• In the absence of an external field,

Degeneracy
MJ J J /cm-1 each of the rotational energy levels has
= 2J +1
5,… …,-5 11 5 30𝑩 a degeneracy of (2J + 1) with the
different sub-levels being distinguished
by a quantum number MJ which takes
4,……,-4 9 4 20𝑩 values from +J to –J.
3,……,-3 7 3 • J defines the number and the
12𝑩
magnitude of angular momentum the
2,……,-2 5 2 6𝑩
rotor possesses, MJ defines how it is
1,0, -1 3 J=1 2𝑩
oriented.
0 1 J=0 0𝑩
 Magnitude and direction of angular momentum
• Energy for the rotor = kinetic energy only = ½I2 = L2/2I
but E = ћ2J(J+1)/2I  L2 = ћ2J(J+1)  |L| = 𝑱(𝑱 + 𝟏)ħ

• The value of MJ defines the component of the angular momentum along a

given reference axis, e.g., z axis with Lz = MJħ.
|L| = 6ћ
For J =1: |L| = 𝟐ћ For J =2:
Unit in ħ Unit in ħ
MJ =+1 MJ =+2
MJ =+1
MJ = 0 MJ = 0
MJ =–1
MJ =–1
MJ =–2
 Populations of the different energy levels
• Rotational energy levels are close enough in energy that many are occupied at R.T., i.e.
a given sample will have molecules rotating at various different frequencies.

• The populations of the different rotational T = 300 K

B = ћ2/2I
energy levels are given by the Boltzmann
distribution.

• The ratio of NJ, the population of the Jth

level, to N0, the population of the ground
state (J = 0) is given by:

𝑵J 𝑵𝟎 = 𝒆−𝑬/𝒌𝑻 (𝑬 = 𝑬𝑱) ?

𝒉𝒄𝑩𝑱(𝑱+𝟏) Yet this is incorrect without
 𝑵J 𝑵𝟎 = exp( )
𝒌𝑻 considering the degeneracy!
 Effects of the degeneracy of energy levels
• Taking the different degeneracies (i.e., 2J +1) of the energy levels into account, the
populations of the different energy levels is given by:
population  (2J+1) exp(EJ/kT)  [(2J+1) exp(EJ/kT)]/J = 0
 𝑵J 𝑵𝟎 = (2J+1)exp(
𝒉𝒄𝑩𝑱(𝑱+𝟏)
)  Jmax
𝒌𝑻
• Overall the population of the
different levels rises to a maximum
and then decreases.
• The value of J for the energy level
with the maximum population,
Max.
denoted Jmax, may be found to be:
population
𝒌𝑻 𝟏 for J =7
𝑱𝒎𝒂𝒙 ≈ −
𝟐𝒉𝒄𝑩 𝟐 Ex.13
 Transition between rotational levels Ex.8

Molecules can be promoted from one rotational energy level to the next with the absorption of a
photon but there are certain restrictions. For the rigid diatomic rotor the selection rules are:
1. The molecule must possess a permanent dipole moment to absorb EM radiation.
2. During the transition J must change by ±1 only (i.e. ΔJ = ±1). J = 𝑩J(J+1), J = 0,1,2,3,…
3. There are also restrictions on ΔMJ but these are less important.

Allowed transitions For a diatomic rotor The rotational spectrum for N2O

𝒉
=12𝐵 12B 𝒓=
𝟖𝝅𝟐𝒄𝑩
=10𝐵 10B
=8𝐵 8B
~0.83 cm-1
=6𝐵 6B
=4𝐵 =4B
=2𝐵 =2B
B = 0.42 cm-1
equal spacing of lines！ 2B
Final spectrum
Freq.
2B 4B 6B 8B 10B 12B
 Intensities of the spectrum lines
• The relative intensities of the peaks depend on the populations of the energy levels.
• The intensities of the peaks in the spectrum first rise with increasing J and then fall off again.
• The relative intensities of the peaks in the spectrum are not determined solely by
the populations of the energy levels.
• For example, when the higher rotational energy levels are occupied, emission processes (both
stimulated and spontaneous) need to be taken into account as well as absorption.
• As a result, whilst the maximum population for a rotational level for CO is J =7, the most
intense peak actually is due to the transition J = 12 → 13.
 Polyatomic molecules
For linear polyatomic molecules, the spectra have the same form for the diatomic molecules.
• The peaks are still separated by 2B, from which the moment of inertia can be deduced!
•  bond lengths ! More info. needed. rco+x rcs-x
rco < rcs O C S
For example: carbon oxysulphide, O=C=S. Centre
of mass

The molecule balances on its centre of mass.  mCx + mO(rCO +x ) = mS(rCS - x )

The moment of inertia is the sum of the moments of inertia of each atom rotating about the
centre of mass. It is given by: I = mCx2 + mO(rCO+x )2 + mS(rCS - x )2
Eliminating x from both equations gives,
I = mOr2CO + mSr2CS  (mOrCO  mSrCS)2/M (M = mS + mC + mO )

While I can be deduced from B, both rCO and rCS are to be determined! Yet need more info.
 Isotopes substitution
Thus in the above example, if we measured B for 18O=C=S and calculated the new moment of
inertia, I', we would have a second equation where the only unknowns were the two bond
lengths, rCO and rCS, which we assume are unchanged.

I' = m18Or2CO + mSr2CS  (m18OrCO  mSrCS)2/M (M = mS + mC + m18O )

Solving the equations for I and I' allow the bond lengths rCO and rCS to be determined.
 4 Rotational Raman spectroscopy
In order for a rotor to absorb electromagnetic radiation, it must have a dipole moment. So, for
example, whilst CO will absorb in the microwave region of the spectrum N2 will not.
 Raman spectroscopy can be used to circumvent the aforementioned drawback.
scattering

If light is passed through a transparent substance, most passes straight hv hv

sample
through, unchanged, but some is scattered at different angles.

Most of the scatter light is Rayleigh scattering, having the same freq. as the incident light.

Some of the scattered light has frequencies greater or less than that of the incident light.

 How to understand and to further make use of such phenomena?

 4 Rotational Raman spectroscopy hv
sample
hv

scattering
No explicit
transition
but inducing a
dipole!
Xhigher J + lower freq. light (Stokes)
Incident
XJ + laser light [XJ] XJ + same freq. light (Rayleigh)
(freq.)
Molecule in
virtual state
rotational level J Xlower J + higher freq. light (anti-Stokes)

The selection rules for a linear molecule in Raman spectroscopy are: J = 0, ±2

Note: J is defined by convention as J(upper level) –J(lower level) and thus is always positive!
 4 Rotational Raman spectroscopy
A schematic diagram for some allowed transitions and the resulting Raman spectrum
Let J = Jlower & Jupper =J +2,
J = Jupper – Jlower
=22B
= 𝐵(4J+6) cm-1
=18B
Stokes lines appear at:
=14B
incident – 𝐵(4J+6) cm-1
=10B
(J = 0,1,2,…)
=6B
Anti-Stokes lines appear at:
Stokes branch Anti-Stokes branch
incident + 𝐵(4J+6) cm-1
4B 6B 6B 4B 4B
(J=0,1,2,…)
Freq.
Subscription S4 S3 S2 S1 S0 S0 S1 S2 S3 S4
is J(lower) Incident
freq.i
 The frequencies of the transitions observed in Raman spectrum are given by:

J = Jupper – Jlower= 𝐵Jupper (Jupper+1) – 𝐵Jlower (Jlower+1) (Let Jlower = J,

then Jupper = J+2)
= 𝐵(4J+6) cm-1
Rayleigh
Anti-Stokes Stokes
Stokes lines appear at:

incident – 𝐵(4J+6) cm-1 (J = 0,1,2,…)

Anti-Stokes lines appear at:

incident + 𝐵(4J+6) cm-1 (J=0,1,2,…)

The pattern of intensities will be discussed later.

Ex.14,15 Raman spectrum of 15N

2
 5 The vibrating rotator
Now we are able to understood the fine structure in the IR spectrum of CO.
The peaks in the IR spectrum correspond to the same vibrational transition (v 1 0);
 For each peak there is a different change in the rotational energy.
 The selection rules for a simultaneous change of both vibrational energy and
rotational energy in a diatomic molecule are: Δv = 0, ±1, ±2, ±3, . . ., etc. ΔJ = ±1.

• Δv = 0 ~ solely rotational transitions.

• ΔJ = 0 is impossible for a diatomic mol.!

Pure vibrational transition is absent in the
spectrum. Each vibrational change must be
P-branch Q-branch
accompanied by change in rotational energy!
 Fine structures in IR spectrum
Rotational
• The lines to the low frequency side of the band levels with
origin are designated the P-branch whilst those the same
vibrational
to the high frequency side are designated the R-
state v =1
branch.

Lines arising from

ΔJ = 2, 1, 0, +1, +2
called O P Q R S branch Rotational
levels with
Seen in Raman the same
vibrational
• Only the P and R branches are seen in the state v =0
vibrational spectra of diatomic molecules, but P, J =–1 R, J =+1 spacing ~ 2𝐵???
others may appear in the spectra of other ~4𝐵
molecules. Freq.
Subscript Jlower = J P6 P5 P4 P3 P2 P1 R0 R1 R R R4 R
2 3 5
band
origin
 Using the BO approximation, the energy of the vibrating-rotor is simply the sum
of its component parts: Etotal = Evibrational + Erotational

= (v + ½)𝝎 – (v + ½)2𝝎xe + 𝑩J(J+1)

 However, the rotational constant B is not exactly the same in the v= 0 state and the v =1 state.
 The more the molecule vibrates, the greater average bond length <r> becomes. (the larger I) !
 As I  <r>2 & B  1/I  The smaller B for the higher v !
 Define B0 for v=0 and B1 for v=1. Then B0 > B1.
 The spacings in the spectrum are not even; the lines in the R-branch tend to crowd
together with increasing freq. and the lines in the P-branch tend to become more widely
spaced with decreasing freq. (plz confirm this statement!)
The energy for any observable transition:
upper – lower = [(1 + ½ )𝜔 – (1 + ½ )2𝜔x + 𝐵 J'(J'+1)] (𝝎0 = 𝝎 – 2𝝎xe ~ band origin)
e 1
– [(0 + ½ )𝜔 – (0 + ½ )2𝜔xe + 𝐵0J''(J''+1)] = 𝝎𝟎 + 𝑩𝟏J'(J'+1) – 𝑩𝟎J''(J''+1)
 How to derive B1 and B0 from a IR spectrum
The energy for any observable transition is
upper – lower = 𝝎 + 𝑩 J'(J'+1) – 𝑩 J''(J''+1) J+1
𝟎 𝟏 𝟎 
v=1 J J' = J
(𝝎0 = 𝝎 – 2𝝎xe ~ band origin)
J 1
To determine B1, we consider two transitions
PJ+1 RJ-1
with the same J value. J =1 J =+1
 = 𝑹J  𝑷J = 2(2J+1)𝑩𝟏 PJ RJ
J =1 J =+1
e.g., R3P3 = 14 𝑩𝟏

To determine B0, we choose two transitions J+1


with the same J value. v=0 J˝ = J J
J 1
 = 𝑹J-1  𝑷J+1 = 2(2J+1)𝑩𝟎
e.g., R1  P3 =10 𝑩𝟎 Ex.16
(For B1) (For B0)
Once B1 and B0 have been determined, the moments of inertia I (= ℏ2(2B)1) and hence bond
lengths (r=(I/)1/2) in the upper and lower vibrational levels, r1 and r0, may also be found.

The rotational constant for a molecule in a given vibrational energy level, Bv, varies with the
vibrational quantum number, v, according to the following equation:
𝑩v = 𝑩e – 𝜶(v+½)  𝜶 = 𝑩𝟎 − 𝑩𝟏
Hypothetic rotational constant for the a small positive number
molecule with its equilibrium bond length at with the same units as B.
the bottom of the potential energy curve.

Using this expression, once Be has been found from B0 and B1, the equilibrium bond length, re,
(corresponding to the bond length at the minimum of the potential energy curve), may also be
determined.
 6. Normal modes and degrees of freedom
• Imagine a simple string vibrating, such as a guitar string. Usually, the vibration would be
rather more complex, but nonetheless it could still be broken down into combinations from the
fundamental vibration and various contributions from the overtones.

• Similarly, whilst the exact way in which a molecule

fundamental
may be vibrating may be rather complicated, it too
could be broken down into a number of more 1st overtone
simple vibrational modes.
• The molecule (with the exception Composite
of a diatomic) has more than one fundamental vibration
mode of vibration and, as we have already seen,
the overtones in the spectra of molecules are
usually less significant. 2nd overtone
 Degrees of freedom
A N-atom molecule has 3N degrees of freedom, including 3 translational ones, 2 (for linear
molecule）or 3 (for non-linear one) rotational ones, and 3N-6 (for non-linear molecule) or 3N-5
(for linear molecule) normal modes of vibration.
• A non-linear three-atom molecule (e.g., H2O) has 3 normal modes of vibration.

v1 v2 v3

Symmetric stretch bend antisymmetric stretch

3651.7 cm-1 1595.0 cm-1 3755.8 cm-1
The order of the normal modes is based on the symmetries of the vibrations (This will be concerned later).
• A linear three-atom molecule (e.g., CO2) has 4 normal modes of vibration.
+ - +

Symmetric stretch Anti-symmetric stretch Degenerate bending modes

v1 = 1330 cm-1 v3 = 2349.3 cm-1 v2 = 667.3 cm-1
 C-H symmetric stretch
• For an acyclic molecule with N atoms, v1 = 3374 cm-1
there is (N-1) bonds and so (N-1) C-C stretch
stretching modes of vibration. v2 = 1974 cm-1
antisymmetric stretch
e.g., C2H2. v3 = 3287 cm-1
v2
3N-5 = 7 normal modes, including
Degenerate trans bend
N-1 = 3 stretching modes bend v4 = 615 cm-1
2N-4 = 4 bending modes 1595.0 cm-1

Degenerate cis bend

v5 = 729 cm-1
Ex.18
 Perpendicular and parallel vibrations
• To be IR-active, the dipole moment of the molecule must change during the vibration.
e.g., CO2, Never any dipole moment!
 IR inactive!

During the other vibrational modes, the change in the dipole moment may either be
parallel to the principal axis or perpendicular to it.

change in dipole moment

parallel to the principal axis!
No dipole
change in dipole moment
perpendicular to the principal axis!

Q: Which normal modes of C2H2 can be observed in IR spectroscopy？ Ex. 17

 Perpendicular and parallel vibrations J =0

• The selection rules for a simultaneous vibration- J = -1 J = +1

rotation transition in a diatomic molecule (where the v=1
change in dipole moment is parallel to the principle
axis), are
Δv = ±1, ±2, ±3, . . . , etc. ΔJ = ±1 ( ΔJ 0)
v = 1 for all transitions
The selection rule ΔJ = – 1 gives rise to the P-branch J = 1 or 0
and ΔJ = + 1 to the R-branch.

• These same selection rules hold for any linear

molecule, but only for parallel vibrations. v=0

• For vibrations where the dipole-moment change is

perpendicular to the principle axis, the transition may P-branch R-branch
J = -1 J = +1
occur with ΔJ = 0, giving rise to a Q-branch in the
spectrum.
Q-branch
 J =0

The energy of the lines in the Q-branch are given by: J = -1 J = +1

upper – lower v=1

= [(1 + ½ )𝜔 – (1 + ½ )2𝜔xe + 𝐵1J(J+1)]

– [(0 + ½ )𝜔 – (0 + ½ )2𝜔xe + 𝐵0J(J+1)] v = 1 for all transitions
J = 1 or 0
= 𝜔 – 2𝜔xe + (𝐵1 – 𝐵0)J(J+1)
= 𝝎0 + (𝑩𝟏 – 𝑩𝟎)J(J+1)
𝝎0 = 𝝎 – 2𝝎xe ~ band origin v=0

(𝑩𝟏 – 𝑩𝟎)  0
P-branch R-branch
 The lines are not coincident! J = -1 J = +1
 The Q-branch is broadened.
Q-branch
 Perpendicular and parallel vibrations
• The parallel CH stretching mode for HCN is shown below.

The spacing between

R0
P1 - P2,
R1 - R0 etc is ≈ 2𝑩,
P1
R1
R0 - P1 ≈ 4𝑩.
P2
parallel stretch R2
P3 R3
H C N
No Q-Branch

The fact that there is no Q branch means the molecule has to be linear！
 Perpendicular and parallel vibrations
• The perpendicular CH bending mode for HCN is shown below.

Bending  I decreasing

B ∝ 1/I

 B1 > B0 & B1 - B0 >0.

Perpendicular bend
 = 𝝎0 + (𝑩𝟏 – 𝑩𝟎)J(J+1)
H C N Q-Branch

The lines in the Q branch are not all on top of one another as would be the case if B1 =
B0, but spread out on the high frequency side of ω0 as J increases.
 7. Raman spectroscopy revisited: polarizability

• The key point in deciding if a vibration will be Raman active is whether or not there is
a change in the polarizability(极化率) of the molecule.
• When a molecule is put into an electric field, it will be distorted with the nuclei being
attracted towards the negative pole of the field and the electrons being attracted
towards the positive pole.
• This distortion therefore sets up an induced dipole moment in the molecule and the
molecule is said to be polarized. The size of the induced dipole moment, μ, is
proportional to the strength of the electric field, E.
 = E  ~ polarizability of a molecule
• How polarizable an atom or molecule is depends on how easy it is to distort its
electron cloud.
 7. Raman spectroscopy revisited: polarizability
Average polarizabilities of some atoms and molecules
without permanent dipole moment

Electrons more
easily distorted!
 Larger !

increasing Zeff
smaller, more compact atom, harder to distort, smaller 
 7.1 Dependence of Polarizability
Why do we use ‘average polarizability’?
The polarizability varies with how the molecule is aligned in the electric field.
i) Orientation dependence:
easiest to polarize harder to polarize
E E
along the bond axis across the bond axis

ii) Vibration dependence:



x < 0, x = 0, no displacement x > 0,

harder to polarize from equilibrium position easier to polarize x

Thus between the extremes of the vibration, the polarizability of the molecule changes significantly!
This vibration is of course Raman active.
 Example: vibrational modes of CO2
 large change in !
Raman active!
x < 0, x=0 x > 0, no change in !
less polarizable more polarizable x IR inactive!
 no change in !
Raman inactive!
x<0 x=0 x>0
large change in !
equally polarizable d/dx (at x=0) = 0 ! IR active!
(doubly degenerate!)

 no change in !
Raman inactive!
x<0 x=0 x>0 change in !
equally polarizable d/dx (at x=0) = 0 ! IR active!
 Rule of mutual exclusion of molecules having a symmetry centre!
 7.2 Rule of mutual exclusion Ex.19,20

• If a molecule has a center of symmetry (i) then if a vibration is Raman active, it will be
IR inactive and vice versa.

• If there is no center of symmetry, some vibrations may be both Raman and IR active.

This rule could be used to distinguish isomers. e.g., isomers of 1,2-dichloroethene.

Center of symmetry 3N-6 =12 normal modes.

For cis, most are IR/Raman active.

For trans, none can be simultaneously both

IR and Raman active.
 7.3 Words of warning
• Molecules other than linear structures: Most molecules, including simple bent triatomic
molecules have spectra that are very difficult, if not impossible, to interpret fully.

• Overtones and combinations:

i) Occasionally overtones are possible in vibrational spectroscopy.
ii) The normal modes and/or their harmonics for molecules can also combine.
iii) Combination bands arise from the addition of two or more fundamental frequencies
or overtones, such as 1 +/– 2, 1+ 2+/– 3, 21+/–3, etc.
e.g., CO2.
symmetric stretch ν1, ~ 1330 cm-1 interacts Two signals
the 1st overtone (~1334 cm-1) of the bending mode ν2 1285 and 1385 cm-1

itself Raman inactive!

 8. Photoelectron spectroscopy (PES) XPS & UPS

PES can give an indication of the energies of the different occupied orbitals in atoms or
molecules and, in the case of molecules, whether the orbitals are bonding, non-bonding or
antibonding. It is an excellent tool to confirm the predictions from MO theory.
102-104 eV  For atoms, KE = h – Ii
3.3-102 eV KE ~ kinetic energy of the ejected electron.
Ii ~ energy to ionize an electron from ith orbital.

For molecules, part of the photon energy

can also promote the ion to a higher
vibrational-rotational state.
KE = h – Ii – Evib – Erot
PES thus can also reveal information
concerning the vibrational energy levels in
the resulting ion.
(©AG Jacobs)
 8.1 Ionization energy vs. orbital energy

The ionization energy is not simply equal to minus the corresponding orbital energy but the
difference in energy between the starting material and the product,

For M  M+ + e–: Ii = Eelectrons(M+) – Eelectrons(M)  i

(i ~ energy of the ith orbital from which the electron was ejected.)

Whilst not exact, the ionization energies are a good indication of the energies of
molecular/atomic orbitals.
 8.2 Photoelectron spectra of atoms
The PES of neon gas:
• Three peaks -- removal of an electron from the 1s, 2s and 2p orbitals, respectively.
• The ratio of the peaks: 2s:2p  1:3

Ne+ (1s22s22p5)
Ne+ (1s22s12p6) Ne+ (1s12s22p6)
 8.2 Photoelectron spectra of atoms Ii = Eelectrons(M+) – Eelectrons(M)

When looking at the PE spectra of atoms, we should really use the term symbols to represent the
different levels of the ions produced. This is essential when spin-orbit coupling becomes
significant, e.g., PES of Krypton ([Ne]3s23p63d104s24p6).

Kr+ …3s13p6… …3s23p5… …3p63d9… …4s14p6… …4s24p5…

3p 2P 3d 2D5/2 4p 2P3/2 & 2P1/2

J = |L+S|,…,|L-S| 3/2
3d 2D3/2
3s 2S 3p 2P1/2
1/2
4s 2S1/2

lower IE corresponds the state of lower energy of the cation.

 8.2 Photoelectron spectra of atoms Ex.21

The degeneracy of a given level is given by the general formula (2J + 1) – the degeneracies are
the main contributor to the observed intensity ratio of the peaks in the PE spectrum.
2 P : 2P = 4:2
3/2 1/2

Two factors influence the magnitude of

the spin-orbit coupling.
14.0
i) the nuclear charge Z – the greater Z, 0.6
the greater the coupling. 14.6 (not resolved)

e closer to n
ii) the e-n separation – the further away 214.4
the electron, the smaller the interaction. 7.8
222.2
The energies of the different levels formed on 1679.3
removing an electron from the p orbitals in 52.5
1731.8
krypton are given here.
 8.3 Photoelectron spectra of molecules
The PE spectra for molecules show a series of bands, each consisting of a number of peaks
corresponding to the removal of an electron from a particular molecular orbital.

 Some of the energy of the incident H2 (1g2)  H2+ (𝑋2g+, 1g1) + e–

photon is used to vibrationally excite
 − 6𝜔𝑥𝑒 2  − 4𝜔𝑥𝑒
the ion.
3 1
4 0.272eV
 The different peaks in the spectrum v' = 0 = 2190 cm-1
of H2 correspond to the final ion 5
6
being left in different vibrational 8 7 =  − 2𝜔𝑥𝑒
9
states.
H2+ (10)~ 2190 cm-1
N2 15.426
H2 (10) ~ 4159 cm-1
The change in bond strength, bond length etc?
* NIST webbook
Why does the v=2 state give the highest intensity?
 8.3.1 The Frank-Condon principle
• The time needed for the photoelectron effect to take place is extremely short – of the order of
femto seconds (10-15 seconds), much quicker than the time of vibrating.
• Consequently, during the electronic transition there is no appreciable change in the geometry of
the molecule, i.e the bond length stays the same. This is known as the Franck-Condon principle.

 At room temperature, the only significantly populated vibrational

level for the neutral molecule is the v'' = 0 level. The probability
density for this level is at a maximum for bond lengths near to the
equilibrium separation, re.
 Since the bond length does not change during the electronic
transition, the only levels that can be populated in the cation
immediately after ionization are those whose population densities
have maxima at this same separation.
 8.3.1 The Frank-Condon principle
• In the PE spectrum of H2, the peak with the maximum p.e. curve for H2+
intensity is not the one where the ion is left in the
𝑋2g+ D0
vibrational ground state (with v'= 0), but in a vibrational
= 2.65 eV
excited state (with v'= 2). 2190 cm-1
re =106 pm
• Since the left-edge of the potential curve rises steeply at
short bond lengths, there are a number of higher vibrational
p.e. curve for H2
energy levels with their maxima around the bond lengths
indicated by the shaded bar. X1g+
v' = 2
v' = 1
v' = 0 D0
= 4.75 eV

4159 cm-1

re =74 pm
 The Frank-Condon principle
(More cases)
In case the internuclear separation in the ion is the same as Same re in
mol. and ion.
that in the neutral molecule (i.e., electron ejected from a
non-bonding MO), the most likely transition upon
ionization is to the vibrational ground state in the ion. Few
peaks can be seen in the PE spectrum!

In case the bond length in the ion is shorter than the
neutral molecule (i.e., electron likely ejected from an anti- Shorter re
in ion.
bonding MO), few peaks can be seen in the PE spectrum.
 The PE spectrum of N2
N2 X1g+ (… 2g2 2u21u4 3g2) These peaks can be observed in the PES
~ 2345 cm-1 spectrum of H2 with N2 inpurity.

2u~ weakly antibonding 1u ~ strongly bonding 3g ~ relatively weakly bonding
𝐴 2 u 𝑋2g
𝐵2u
(u3) (3g1)
(2u1)
0.224 𝑒𝑉
= 1810 𝑐𝑚-1
0.260 𝑒𝑉
0.296 𝑒𝑉
= 2100 𝑐𝑚-1
= 2390 𝑐𝑚-1
 Summary
• Vibration of diatomics can be modelled by either harmonic oscillator (v = (v + ½)𝝎) or
the more realistic Morse oscillator (v = (v + ½)𝝎 – (v + ½)2𝝎𝒙𝒆).
• Selection rule for an allowed transition: i) H.O. ~ dipolar, v = 1;
VHO(x) = kx2/2 ii) M.O. ~ dipolar, |v| 1;
VM(x) = De [1  exp (βx)]2
• For H.O.: Ev+1v = ħ𝝎 vv-1 = 𝝎

• For M.O. : 𝒗𝒎𝒂𝒙 = (xe-1 -1)/2

𝑫e (in cm-1) = 𝝎(4xe)-1
De
BDE = D0 Ev v-1 = ћω  2ћωxe
vv-1 = 𝝎 − 2𝒙𝒆𝝎
0= De - D0
 Summary
• Molecular rotation can be modelled by rigid rotor (I = r2, EJ= BJ(J+1), B = ħ2/2I, B=𝒉𝒄B).
𝒉𝒄𝑩𝑱(𝑱+𝟏)
𝑵J 𝑵𝟎 = (2J+1)exp( )
𝒌𝑻

• Transitions between rotational energy levels in molecule can be observed:

i) in microwave spectrum with the Selection rule (dipolar, J = 1) and peak distance of 2B.

ii) in rotational Raman scattering spectrum with the selection rule (lineal molecule): J =0,
2, and as Stokes lines and anti-Stokes lines by 𝟒𝑱 + 𝟔 𝑩 cm-1 lower and higher than the
incident line, respectively.

iii) as fine structures in vibrational IR spectrum: with the selection rule: J = 1 (for
diatomics) and J = 0 for dipole moment change perpendicular to the principle axis.
The End of Molecular Spectroscopty
 吸收： 自发发射： 受激发射
M + h  M* M*  M + h M* + h  M + 2h
E

h h h 2h
Energy (cm1)
Energy (cm1)

电子第一
激发态

电子基态

每个电子态有许多振动能级 每个振动态有许多转动能级