Rotational & Vibrational

Spectra
 The total angular momentum squared is J2 = J(J+1) 2 and the rotational
energy EJ = J2/2I = J(J+1) 2/2I
The moment of inertia, I = Re2 for a diatomic molecule. In the rigid rotor
approximation, Re is taken to be the average, or equilibrium bond distance,
which could be calculated, for example, from the zero-point wavefunction of
the harmonic oscillator. We define a rotational constant, B, such that:

The last part here applies

only to a diatomic
h2 h2 h2 molecule, whereas the
B= = = Joules concept of B applies to all
2 I 8 2 I 8 2 Re 2 molecules. (See later)
h -1 h -1 8 -1
= sec = cm c=2.9979 10 msec
8 2 I 800 2 Ic

12/6/2016 Vibration-Rotation Spectra 2

Energies of Microwave Transitions See sections 5-8 & 5-9

The rotational selection rule J=+1 for microwave absorptions gives us:

Erot = Bh( J + 1)( J + 2) BhJ ( J + 1) = 2 Bh( J + 1)

Here, the context shows that the units of B are
sec-1. Always inspect the dimensions to
determine the correct units to use..

So, although the energy levels are not uniformly spaced, the microwave
transitions are.
The rigid rotor approximation needs to be assumed. This is better than the
harmonic oscillator approximation for vibrations, but high rotational energy
does lead to measurable extension of the bond, by centrifugal distortion. We
do not need to make this correction at this level.

12/6/2016 Vibration-Rotation Spectra 3

Despite the simple selection rule (J=1), absorption spectra contain many
resonances derived from rotation. This is because many rotational levels are
Here, B is taken to be in
populated at room temperature. units of sec-1

EJ hBJ ( J + 1)
N J g J exp = (2 J + 1) exp
k BT k B T
This gives the relative population, NJ of the different J states.
Recall that each J-level has 2J+1 MJ sublevels, which are taken into account as the
statistical weight gJ. To establish a reference, we need to sum over all populated
levels, which gives us the partition function:

  + 1

 =   = (2 + 1) exp


The temperature dependent partition function, q(T), is important in Chem 222

(see Section 18.5 and Figure 18.5).

12/6/2016 Vibration-Rotation Spectra 4

 Note figure from Ch 18, which describes the normalized population distribution
function:


=

12/6/2016 Vibration-Rotation Spectra 5

 0.12

200 K
0.1

Normalized Relative Population

f200J 0.08
300 K
MathCAD
normalized f300J 0.06 400 K
relative f400J
population 0.04
for CO
0.02

0
0 5 10 15 20 25 30 35
J
Rotational Quantum
Rotational Number
Quantum Number

The weighted Boltzmann distribution (weighted by gJ=2J+1) corresponds

closely to the envelope of rotational transitions observed in the microwave,
rotational Raman and IR spectra.

12/6/2016 Vibration-Rotation Spectra 6

Analogy between the rotational selection rule for diatomic molecule and that
for electronic transitions in the H-atom

See supplement on transition moments.

12/6/2016 Vibration-Rotation Spectra 7

Vibration-rotation spectroscopy (see Section 13.2; Section 18.5, Eq. 18.35)
Energy of ro-vibrational levels in the rigid rotor, harmonic oscillator model for
diatomic molecules:
1
E = v + h + hBJ ( J + 1) = EV + hBJ ( J + 1)
2
A typical infrared transition is denoted as follows:

E = ( EV ' EV ") + hB ' J '( J '+ 1) hB " J "( J "+ 1)

Single primes refer, by convention, to the higher-energy vibrational level, and

the double primes refer to the lower vibrational level.
Usually, because of anharmonicity, r' > r", so that B" > B' Note that for a
diatomic molecule:
h
B(sec1 ) =
8 2 r 2

12/6/2016 Vibration-Rotation Spectra 8

 Atkins diagram
First vibrational level
unique for a diatomic Q
molecule, but there J values
could be many such

{
levels for a larger
molecule.
(3n-6 in general)

P-branch R-branch
J= -1 J= +1

Vibrational Ground State J values

- unique for all molecules

12/6/2016 Vibration-Rotation Spectra 9

For vibrations, as we have seen before, the Harmonic Oscillator selection rule is
v = 1. In addition, the rotational selection rule for diatomic molecules with
no unpaired electrons is: J=1. So that we have:
P branch J' = J" - 1
R branch J' = J" + 1
Conspicuously missing is the:
Q branch J' = J"
which can only be seen if there is electronic or vibrational angular momentum
associated with the molecule. That means that the Q branch can be seen for
diatomic molecules with unpaired electrons, such as NO, or for larger
molecules - see later.

Of course, for vibrational transitions to be observed, a diatomic molecule must

have a permanent dipole moment.

12/6/2016 Vibration-Rotation Spectra 10

 86 12 16
% Transmission
Q-branch missing C O

84

P-branch R-branch

P-branch diverges as R-branch converges as

displacement increases displacement increases
82
2050 2100 2150 2200
-1
Wavenumber (cm )
12/6/2016 Vibration-Rotation Spectra 11

E = h for all three branches

P-branch
EP = EV + hB ' J '( J '+ 1) hB " J "( J "+ 1)
= EV + hB '( J " 1) J " hB " J "( J "+ 1) substitute J-1 = J

= EV + hJ "2 ( B ' B ") hJ "( B '+ B ")

Q-branch
EQ = EV + hB ' J '( J '+ 1) hB " J "( J "+ 1)
= EV + hB ' J "( J "+ 1) hB " J "( J "+ 1) substitute J = J

= EV + h( B ' B ")( J "2 + J ")

R-branch

ER = EV + hB ' J '( J '+ 1) hB " J "( J "+ 1)

= EV + hB '( J "+ 1)( J "+ 2) hB " J "( J "+ 1) substitute J+1 = J

= EV + hJ "2 ( B ' B ") + hJ "(3B ' B ") + 2hB '

12/6/2016 Vibration-Rotation Spectra 12

If the molecule were a harmonic oscillator and a rigid rotor, the vibrational
quantum number would not affect the average internuclear spacing:
then B' = B". This would result in the following:

EP = EV 2 BhJ "
EQ = EV
ER = EV + 2 Bh( J "+ 1)
The P and R-branches would consist of equally spaced lines heading in
different directions (R branch to higher energy and P to lower energy),
whereas the Q-branch would be a single line.

12/6/2016 Vibration-Rotation Spectra 13

In the real case for vibration-rotation
transitions, B" > B', so that:
The P branch diverges Harmonic oscillator
The Q branch lines diverge slowly
towards the P branch
Real case
The R branch converges

Why is B" > B ? Because r < r.

This is because the bond tends to
stretch with increasing vibrational
energy, so that B tends to decrease.

12/6/2016 Vibration-Rotation Spectra 14

Real diatomic molecules show convergence in the R branch and divergence in
the P branch because the bond length increases in the upper vibrational level
(i.e., r<r; B>B). Doubling of resonances occurs because of the two isotopes of
chlorine.
DCl

80
Transmission

1 0
R branch
70 P branch

2
1
3
2
1900 2000 2100 2200
-1
12/6/2016
Wavenumber (cm )
Vibration-Rotation Spectra 15
Band Doubling due to Multiple Isotopes
The bands are all doubled in natural HCl and DCl , because of the
natural isotopic mixture of 35Cl and 37Cl. There is roughly three times as
much of the lighter isotope, 35Cl. This is seen better in the DCl trace at the
available resolution, because the splitting is a little larger.
If we assume for the sake of illustration that the molecule is a
harmonic oscillator, then we can use the following equation to estimate the
vibrational frequency.
1 k
=
2
If we assume that the only change in vibrational frequency is due to the
difference in reduced mass, we can write for the HCl case:

( H 35Cl ) ( H 37Cl ) 0.9737

37
= 35
= 1.00075
( H Cl ) ( H Cl ) 0.9722

12/6/2016 Vibration-Rotation Spectra 16

Taking ~ 2900 cm-1 for HCl, we predict a difference of ~2.2 cm-1, which is close
to the experimental resolution.
The reduced mass ratio for the two isotopomers of DCl is slightly greater:

( D 35Cl ) ( D 37Cl ) 1.8974

37
= 35
= 1.00146
( D Cl ) ( D Cl ) 1.8919

Taking ~ 2100 cm-1 for DCl, we predict a difference of ~3 cm-1. This difference
between the DCl and HCl spectra is enough to show a marked improvement in
the resolution of the DCl spectrum.

Go to worked example on DCl

12/6/2016 Vibration-Rotation Spectra 17

Parallel and Perpendicular Bands
For triatomic and larger linear molecules, there are two distinct types
of vibrational mode seen in the IR spectrum, recognizable by their shapes.

A vibrational mode must have a symmetry corresponding to that of an

electric dipole vector in order to be seen in the IR spectrum.

For a linear molecule, symmetry rules require that an incident photon

be absorbed according to its polarization parallel or perpendicular to the
molecular axis. This gives rise to the notation parallel and perpendicular
bands.

Parallel band - change of dipole moment during vibration is parallel to

the molecular axis -- photon incident at a right angle to the molecular axis,
electric field oriented parallel to the axis, angular momentum directed
perpendicular to the axis.

Has only P & R branches, like most diatomic molecules. Also typical of
stretching modes of linear polyatomic molecules such as CO2 and C2H2.

12/6/2016 Vibration-Rotation Spectra 18

 Perpendicular band - change of dipole moment during vibration is
perpendicular to the molecular axis - photon incident along the molecular axis,
electric field oriented perpendicular to the axis, angular momentum directed
along the axis.

Has P, Q & R branches, unlike most diatomic molecules. Typical of

bending modes of linear polyatomic molecules such as CO2 and C2H2

12/6/2016 Vibration-Rotation Spectra 19

Vibrational Modes of CO2

1 - IR inactive 2 - IR active
(doubly degenerate)
Perpendicular band, P, Q, R

3 - IR active
Parallel band, P, R

12/6/2016 Vibration-Rotation Spectra 20

No Q-branch for this parallel band of CO2 - antisymmetric stretch.

CO2 - 001

80
% Transmission

70

60

50

2300 2325 2350 2375

-1
Wavenumber (cm )

12/6/2016 Vibration-Rotation Spectra 21

The perpendicular band of the bending mode shows a strong Q-branch

P-branch R-branch
80

60
Transmission %

Hot band
Q-branch Hot band
Q-branch
40

13
Q-branch for CO2
12
20 ~1% natural abundance CO2

Q-branch
0
600 625 650 675 700 725
-1
Wavenumber (cm )

12/6/2016 Vibration-Rotation Spectra 22

Why is there a Q-branch for the bending mode?

Consider what we know about the bending mode. There is a displacement

simultaneously along two axes (x,y) perpendicular to the molecular axis (z).

In the point group  , the x and y axes form a degenerate pair. However, we
encounter a situation resembling that of the molecular -orbitals, which on the
one hand could be viewed as x and y. But on the other hand, could be viewed
as 1, using the angular momentum notation. Since spectroscopic properties
rely on angular momentum conservation, we find the interpretation of the Q-
branch in these terms.

Thus, the ground state of the O2 molecule has triplet spin, but cancelling orbital
angular momentum, leading to the 3 term symbol. A similar situation applies
to the bending mode of the vibrating CO2 molecule.

In the zero-point state, the vibrational quantum number is zero and there is
zero angular momentum to assign about the molecular axis.
In the v=1 state, we cannot say which of the bending mode components has the
energy, but we do know that the component of angular momentum about the z-
axis is m=1.
23
Nuclear Spin Considerations
For homonuclear, homoisotopic diatomic molecules (e.g., 16O2 or
18O but not 16O18O), and a number of other symmetrical species (CO2, CH4,
2

C2H2), nuclear exchange properties control the rotational level populations.

Nuclei having a non-integer spin quantum number, such as

electrons, protons and neutrons, including 1H and 3He nuclei, must have a total
wavefunction that is antisymmetric with respect to exchange of the particle
labeling. These entities, which also should be noted to contain an odd number
of nucleons, are known collectively as Fermi-Dirac particles.

Particles having integer spin quantum numbers (i.e., containing an

even number of nucleons), such as photons, 2H, 4He, 14N and 16O nuclei, must
have a total wavefunction that is symmetric with respect to exchange. These
are known as Bose-Einstein particles.
12/6/2016 Vibration-Rotation Spectra 24
 The total wavefunction for a molecule has four distinct components:

TOTAL = E V R N
For a molecule such as 1H2 (normal hydrogen), the equivalent nuclei are
Fermi-Dirac (spin ) particles. They require TOTAL to be antisymmetric
with respect to exchange of labeling. This means that the product of the
symmetries of the four component wavefunctions needs to be antisymmetric.

For molecules such as 2H2 (a.k.a. D2), 14N2, 16O2, C16O2 and others, the
equivalent nuclei are Bose-Einstein (integer-spin) particles. They require
TOTAL to be symmetric with respect to exchange of labeling. This means that
the product of the symmetries of the four component wavefunctions needs to
be symmetric.

12/6/2016 Vibration-Rotation Spectra 25

For CO2 specifically, we have the situation

TOTAL = E V R N
E - symmetric electronic ground state - this is normal.
V - symmetric vibrational ground state - again normal.
R - symmetric for even-J; antisymmetric for odd-J
N - can only be symmetric, because I=0 for 16 O

Because there are no antisymmetric nuclear spin states for this molecule, only
even-J rotational levels can exist: J = 0, 2, 4, 6
For a molecule such as N2O, which has no symmetrically equivalent atoms, all
J-levels are present, giving us a more congested spectrum. (See next slide).

12/6/2016 Vibration-Rotation Spectra 26

IR absorption spectrum of CO2 and N2O

CO2 N2O
Transmission increasing

Spacing of rotational
lines in CO2 is twice
that of N2O, because
half of the ground-state
rotational levels are
missing in CO2

12/6/2016 Vibration-Rotation Spectra 27

Normal acetylene 1H12C
C2H2 4+125 C1H
85

% Transmission 80

75

70

65

1250 1300 1350 1400

-1
Wavenumber (cm )

The rotational level structure in 12C21H2 is weighted by the exchange of protons. Since protons
are spin particles, the combined spin states can be either singlets (antisymmetric) or triplets
(symmetric). This leads to a 3:1 alternation in the effective absorption intensity on different
rotational levels. This is readily seen in the IR spectrum note that acetylene doesnt have a
12/6/2016 Vibration-Rotation Spectra 28
microwave spectrum because it has no dipole moment.
Bond
Lengths in
CO2

Note that the line spacing is 4B, not 2B for C16O2

12/6/2016 Vibration-Rotation Spectra 29

Why do we see a Q-branch for the bending modes of linear molecules?
The J=1 selection rule, giving the P and R branches arises from
conservation of angular momentum when a photon is absorbed.
The J=0 condition that allows a Q-branch implies that angular momentum
can be accommodated by some other means. In the case of CO2 and acetylene (see
below), this involves vibration. So a vibrational motion can involve angular
momentum.
The bending modes are doubly degenerate, and if we combine them in a
certain way, we can readily demonstrate this phenomenon.

12/6/2016 Vibration-Rotation Spectra 30

 Go to movies

12/6/2016 Vibration-Rotation Spectra 31

A vibration in the direction of the molecular axis has zero angular momentum
about that axis. (Such a vibration forms the basis for a -type representation in a
linear point group). This is also true of the vibrational ground state (zero-point
level), which is the starting point for normal infrared absorption spectra.

The doubly degenerate bending modes have angular momentum quantum

number m = 1 in the v=1 state, which is directed along the molecular axis. Such
modes form the basis for -type representations.

(We have seen the formula = eim in another context, and this applies here).

Note that we need a linear combination, because we cannot know which of the x-
or y-axis bending vibrations has the energy. The linear combination involving a
/2 phase shift between the two components gives the correct form for right- or
left-circulation.

12/6/2016 Vibration-Rotation Spectra 32

Now that we can change the angular momentum by exciting a vibrational
motion, it is possible to change the angular momentum without changing the
rotational quantum number, J.

In summary, the doubly degenerate bending mode provides a way to accommodate the
photon angular momentum, which therefore permits the J=0 transition. This accounts
for the strong Q-branch.

12/6/2016 Vibration-Rotation Spectra 33

The perpendicular band of the CO2 bending mode shows a strong Q-branch

P-branch R-branch
80

60
Transmission %

Hot band
Q-branch Hot band
(v=2 v=1) Q-branch
40
(v=2 v=1)
13
Q-branch for CO2
12
20 ~1% natural abundance CO2

Q-branch
0
600 625 650 675 700 725
-1
Wavenumber (cm )

12/6/2016 Vibration-Rotation Spectra 34

Methane
Two fundamental bands only, each showing, P, Q and R structures.

T2 bend
1306 cm-1
T2 stretch
3020 cm-1

12/6/2016 Vibration-Rotation Spectra 35

Methane and CCl4 both belong to the Td point group (regular tetrahedron).

Td E 8C3 3C2 6d 6S4

Activity

A1 1 1 1 1 1 x2+y2+z2 Raman only

A2 1 1 1 -1 -1

E 2 -1 2 0 0 (x2+y2-2z2, x2-y2) Raman only

T1 3 0 -1 -1 1 (Rx,Ry,Rz)

T2 3 0 -1 1 -1 (x,y,z)(xy,xz,yz) Raman and IR

red 15 0 -1 3 -1 A1+E+T1+3T2

vib 9 0 1 3 -1 A1+E+2T2

There are 5 atoms, leading to 15 degrees of freedom, 9 of which are in vibrational

modes.
There are only 4 distinct vibrations because the E-type accounts for 2 and the two
T2 modes account for 3 each.
Only the T2 vibrations are active in the IR. All three types are seen in the Raman
spectrum.
12/6/2016 Vibration-Rotation Spectra 36
CCl 4 Vibrat ional dat a from ht t p:/ / webbook.nist .gov

12/6/2016 Vibration-Rotation Spectra 37

Raman Spectrum of CCl4 - recorded by Chem 223 students

375
antiSTOKES STOKES
275 e a1 { polarized Parallel
polarizat ion
175
t 2 (f 2 )
a1
75

-25
500 510 520 530 540 550 560 570 580 590 600
200

150

Perpendicular
100
polarizat ion
50

0
500 510 520 530 540 550 560 570 580 590 600
12/6/2016 Vibration-Rotation Spectra 38
-50
12/6/2016 Vibration-Rotation Spectra 39
 Mode Raman Detected Wavelength Polarized Scattering ?
shift (nm)
(cm-1)
a1 (antiStokes) +459 519.4 Y

t2 (antiStokes) +314 523.4 N

e (antiStokes) +217 526.0 N

Laser (and Rayleigh) 0 532.1 Y

e (Stokes) -217 538.3 N

t2 (Stokes) -314 541.1 N

a1 (Stokes) -459 545.4 Y

t2 (Stokes) -776 555.0 N

12/6/2016 Vibration-Rotation Spectra 40

Summary for CCl4 in the condensed phase

Vibrational frequencies are much smaller than for CH4 because of the increased
mass of Cl.

Only the t2 (f2 according to NIST) modes are infrared active

All four frequencies are observed in the Raman spectrum

The Raman signal from the a1 (totally symmetric) mode is polarized and
therefore is only seen when the laser polarization and detector polarization are
parallel.

The signals from lower-symmetry modes are not polarized, and are not
affected by the relative polarization of the laser and detector. Therefore, they are
seen in both spectra.

Significant antiStokes Raman signals are seen from the low-energy modes,
which have energy 1-2 kBT, and are therefore significantly thermally populated in
the v=1 states.

12/6/2016 Vibration-Rotation Spectra 41

n-Decane compare IR vs Raman

IR
5% in CCl4

629 nm
Raman 2890 cm-1
Pure decane

Laser
532 nm 558 nm
1450 cm-1

12/6/2016 Vibration-Rotation Spectra 42

Molecular Fluorescence in Solution is different from Raman scattering in three
important ways:
1. There is only broad band There is little if any detailed structure in the
fluorescence spectrum.
2. The fluorescence spectrum is independent of the exciting laser wavelength,
whereas the Raman spectrum has a constant displacement from the laser.
3. The fluorescence intensity shows a "lifetime" in the nanosecond domain,
whereas Raman emission is coincident with the laser, even into the femtosecond
domain.

12/6/2016 Vibration-Rotation Spectra 43