Lecture 4: Polyatomic Spectra

Ammonia molecule
1. From diatomic to polyatomic A-axis

2. Classification of polyatomic molecules

3. Rotational spectra of polyatomic

molecules
N
4. Vibrational bands, vibrational spectra
H
 1. From diatomic to polyatomic
 Rotation – Diatomics
Recall: For diatomic molecules
F  J , cm 1  BJ  J  1  DJ 2  J  1
2
Energy:  
R. R. Centrifugal distortion constant
h
Rotational constant: B, cm 1 
8 2 Ic
Selection Rule: J '  J "1  J  1

Line position:  J "1 J "  2 B J "1  4 DJ "13

 Notes: _ 2
1. 
D is small, i.e., D / B  4 B / vib  1 
2 2
D  B  1.7 
2. E.g., for NO,    4   4   3  10
6

 B  NO  e   1900 
→ Even @ J=60, D / B  J ~ 0.01
2

What about polyatomics (≥3 atoms)?

2
 1. From diatomic to polyatomic
 3D-body rotation
B

 Convention:
A A-axis is the “unique” or
“figure” axis, along which
lies the molecule’s
C defining symmetry

 3 principal axes (orthogonal): A, B, C

 3 principal moments of inertia: IA, IB, IC
 Molecules are classified in terms of the relative values of IA, IB, IC

3
 2. Classification of polyatomic
molecules
 Types of molecules
Linear Symmetric Asymmetric
Type Spherical Tops
Molecules Tops Rotors
Relative
IB=IC≠IA
magnitudes IB=IC; IA≈0* IA=IB=IC IA≠IB≠IC
of IA,B,C IA≠0

CO2 NH3
H2O
CH4

C2H2 CH3F
Examples
Acetylene
NO2
OCS BCl3
Carbon Boron
oxysulfide trichloride

Relatively simple No dipole moment Largest category

Not microwave active Most complex

*Actually finite, but quantized momentum means it is in lowest state of rotation 4

 2. Classification of polyatomic
molecules
 Linear molecules
E.g., Carbon oxy-sulfide (OCS)
A
B
C
16 12 32

O C S B
A
rCO rCS
rC rS
Center of mass
IB=IC; IA≈0 C
rCO = 1.165Å h
rCS = 1.558Å B, cm 1 
8 2 I B c
5
 2. Classification of polyatomic
molecules
 Symmetric tops
Prolate
IA<IB=IC, A>B=C
A
IB=IC≠IA; IA≠0 E.g., CH3F
h
A, cm 1 
8 2 I Ac B C
h
B, cm 1 
8 2 I B c 1
H B
12 19
H
C , cm 1  2
h
8 I C c
C F
A
H
C.M.
C
Tripod-like (tetrahedral bonding)

6
 2. Classification of polyatomic
molecules
 Symmetric tops  No elec.
dipole mom.
Oblate → no QM

IA>IB=IC, A<B=C
selection rule A
IB=IC≠IA; IA≠0 E.g., BCl3 (Planar)
h
A, cm 1 
8 2 I Ac B
h
B, cm 1  Cl C B
8 2 I B c
11
h 35.5
1
C , cm  2 B
8 I C c Cl
Cl A
B
C.M.
C
C
A Planar view
7
 2. Classification of polyatomic
molecules
 Spherical tops  Asymmetric rotors

IA=IB=IC IA≠IB≠IC
E.g., CH4 (methane) E.g., H2O

H A
 Symmetric, but C
H C
No dipole moment O
H
H H B
No rotational 104.45o
H spectrum
C.M.
Cube w/ C at center C.M.
and H at diagonal  Complex and not
corners addressed here

8
 3. Rotational spectra of
polyatomic molecules
 Linear molecules (IB=IC; IA≈0)
Examples
OCS HCN CO2 C2H2 HC2Cl

Symmetric, no dipole moment

Must be asymmetric to have electric dipole moment (isotopic

substitution doesn’t change this as bond lengths remain fixed)

 Energies and line positions

Can treat like diatomic (1 value of I) → same spectrum
F  J   BJ  J  1  DJ 2  J  1
2

_  Note: Larger I, smaller B

  J   2 B J  1  4 D J  13 (& line spacing)
than diatomics
Rotational Centrifugal
const. distortion const. (” is suppressed, i.e. J=J”)
9
 3. Rotational spectra of
polyatomic molecules
 Linear molecules (IB=IC; IA≈0)
 Bond lengths
N atoms N-1 bond lengths to be found

 Abs./Emis. spectra B 1 value of IB

 Use N-1 isotopes N-1 values of IB

Example: OCS (carbon oxy-sulfide)

O161.165Å C12 1.558Å S32 Use 2 isotopes for 2 equations:

I 16 O12C 32S  F masses, rCO , rCS 
O C S I 18 O12C 32S  F masses, rCO , rCS 
rCO rCS
rC rS
Solve for rCO, rCS
Center of mass
10
 3. Rotational spectra of
polyatomic molecules
 Symmetric tops (IB=IC≠IA; IA≠0)
 2 main directions of rotation → 2 quantum numbers
 J (total angular momentum): 0, 1, 2, …
 K (angular momentum about A): J, J-1, …, 1, 0, -1, … -J
 + & - allowed, w/o change in energy
2J+1 possibilities of K for each J
 Quantized angular momentum J K
As before: I   I   I   J  J  1
2
A
2
A
2
B
2
B
2
C
2
C
2

Plus new: I A A  K 
2 2 2 2

 Energy levels
1
E J , K   I ii2 F  J , K   BJ  J  1   A  B K 2
2 i
 Note degeneracy, i.e., independent of sign of K

11
 3. Rotational spectra of
polyatomic molecules
 Symmetric tops (IB=IC≠IA; IA≠0)
 Q.M. Selection rules

 ΔJ = +1 Remember that J = J’ – J”
 ΔK = 0
No dipole moment for rotation about A-axis
No change in K will occur with abs./emis.

 Line positions

 J .K  F  J  1, K   F J , K   2 BJ J  1 cm 1 

 Note: Independent of K for a rigid rotor

Same as rigid diatomic!
K-dependence introduced for non-rigid rotation

12
 3. Rotational spectra of
polyatomic molecules
 Symmetric tops (IB=IC≠IA; IA≠0) E.g., CH3F, Methyl Fluoride
H
 Non-rigid rotation
H
Effect of extending bond lengths B  0.851cm 1 C F
(w/ changes in K) A
DJ  2  10 6 cm 1
DJK  1.47  10 5 cm 1 H C.M.
Change energies of rotation
If J≈20, J2≈400, 2DJ2≈1.6x10-3, 2DJ2/B≈.2%
J 1 2 3
Centrifugal distortion const. DJ, DK, DJK
2B
~1.7cm-1
F J , K   BJ  J  1   A  B K 2  DJ J 2 J  1
2
ν,cm-1 3 4 5 6 7
 DJK J J  1K  DK K
2 4


 J .K  2 J  1 B  2 DJ  J  12  DJK K 2  cm 
1 K 2 10
2DJK(J+1)K2
3 lines for J=2 ~10-4cm-1
 Note: Each J has 2J+1 components, but K=2,1,0
only J+1 frequencies 2DJK(J+1)K2
~4x10-4cm-1
13
 3. Rotational spectra of
polyatomic molecules
 Symmetric tops (IB=IC≠IA; IA≠0)  gets complex fast!
Prolate Oblate

IA<IB=IC, A>B=C IA>IB=IC, A<B=C

F  J , K   BJ  J  1   A  B K 2 F  J , K   BJ  J  1   A  B K 2
h  1 1 h 1 1
A  B  2     0 A  B  2     0
8 c  I A I B  8 c  I A I B 

Example
energy levels

14
 3. Rotational spectra of
polyatomic molecules
 Rotational partition function

Linear Symmetric top Spherical top Asymmetric rotor

B=C; IA≈0 B=C≠A; IA≠0 A=B=C A≠B≠C
3 3 3
kT 1   kT  1   kT  1   kT 
Qrot  Qrot    Qrot    Qrot   
hcB  AB 2  hc   B 3  hc   ABC  hc 

h σ – molecule-dependent symmetry factor

1
A, cm  2
8 I Ac Molecule σ Molecule Type

B, cm 1 
h CO2 2 Linear
8 2 I B c NH3 3 Symmetric Top
h CH4 12 Spherical Top
C , cm 1 
8 2 I C c H2O 2 Asymmetric Rotor

15
 3. Rotational spectra of
polyatomic molecules: Summary

 Linear (diatomic & polyatomic) and symmetric top

molecules give similar (equal spacing) spectra at
rigid rotor level
 High resolution needed to detect corrections /
splittings
 Spectra → microscopic parameters (re, angles)
 Isotopes useful for spectral studies

16
 4. Vibrational Bands, Rovibrational Spectra

1. Number of vibrational modes Spectrum of bending mode

of HCN
2. Types of bands
 Parallel and perpendicular
 Fundamental, overtones,
combination and difference bands
3. Relative strengths
4. Rovibrational spectra of polyatomic
molecules
 Linear molecules
 Symmetric tops

17
 1. Number of vibrational modes
 N-atom molecule
3N dynamical coordinates needed to specify instantaneous location and
orientation

Total: 3N
Center of Mass: 3 coordinates (3 translational modes)

Rotation: Linear molecules Nonlinear molecules

2 angular coordinates 3 angular coordinates
(rot. modes) (rot. modes)

Vibration: Linear molecules Nonlinear molecules

3N-5 vibrational coordinates 3N-6 vibrational coordinates
(vib. modes) (vib. modes)

18
 4.2. Types of bands
 Numbering (identification) convention of vibrational modes
 Symmetry
 Decreasing energy

[cm-1]
ν1 Highest-frequency symmetric vibrational mode
Symmetric
Declining
ν2 2nd highest symmetric mode
frequency … …
νi Lowest-frequency symmetric mode

Asymmetric νi+1 Highest-frequency asymmetric vibrational mode

Declining νi+2 2nd highest symmetric mode
frequency … …
 Exception: the perpendicular vibration for linear XY2 and XYZ
molecules is always called ν2
19
 4.2. Types of bands
 Parallel and perpendicular modes
Parallel (||) Perpendicular (⊥)
Examples: Dipole changes are || Dipole changes are ⊥
to the main axis of symmetry to the main axis of symmetry

H2O
(3x3-6=3
vib. modes)
Symmetric stretch Symmetric bending Asymmetric stretch
ν1=3652cm-1 ν2=1595cm-1 ν3=3756cm-1

CO2
(3x3-5=4 No dipole moment
vib. modes) Not IR-active!
Symmetric stretch Asymmetric stretch Symmetric bending (2 degenerate)
ν1=1330cm-1 ν3=2349cm-1 ν2=667cm-1
20
 4.2. Types of bands
 Parallel and perpendicular modes
Symmetric molecules: vibrational modes are either IR-active or Raman-active
Vibrational modes of CO2
Frequency
Mode Type Description IR Raman
[cm-1]
ν1 1388 -- Symmetric stretch Not active Active
Symmetric bend
ν2 667 ⊥ (Degenerate)
Strong Not active

ν3 2349 || Asymmetric stretch Very strong Not active

Vibrational modes of HCN

Frequency
Mode Type Description IR Raman
[cm-1]
ν1 3310 || Symmetric stretch Strong Weak
Symmetric bend
ν2 715 ⊥ (Degenerate)
Very strong Weak

ν3 2097 || Asymmetric stretch Weak Strong

21
 4.2. Types of bands
 Terminology for different types of vibrational bands

Fundamental Bands: νi, the ith vibrational mode; Δv=v'-v"=1 for the ith mode

1st Overtone: 2νi; Δv=v'-v"=2 for the ith mode

2nd Overtone: 3νi; Δv=v'-v"=3 for the ith mode

Combination bands: Changes in multiple quantum numbers, e.g.,

ν1+ν2; Δv1=Δv2=1, i.e., v1 and v2 both increase by 1 for
absorption or decrease by 1 for emission
2ν1+ν2; Δv1=2 and Δv2=1

Difference bands: Quantum number changes with mixed sign

ν1-ν2; v1,final-v1,initial= ±1 and v2,final-v2,initial= ∓1, i.e., a
unit increase in v1 is accompanied by a unit
decrease in v2, and vice-versa.

22
 4.2. Types of bands
 Vibrational partition function
 gi

modes
 hce ,i 
Qvib   1  exp  
i   kT 

E.g., NH3: 3N-6 = 6 vib. modes Degenerate

1 1 2 2
  hce,1    hce , 2    hce ,3    hce , 4 
Qvib  1  exp   1  exp   1  exp   1  exp  
  kT    kT    kT    kT 

Vibration Frequency [cm-1] Type Description

ν1 3337 || Symmetric stretch
ν2 950 || Symmetric bend
ν3 3444 ⊥ Asymmetric stretch (Degenerate)
ν4 1627 ⊥ Asymmetric bend (Degenerate)

23
 4.3. Relative strength
 In general
 Fundamental bands are much stronger than combination, difference,
and overtone bands
 Fairly harmonic molecules
 E.g., CO
 Relative strength between fundamental and overtones ~ 102
 Closely SHO, overtone bands are nearly forbidden (low transition
probabilities)
 Highly anharmonic molecules
 E.g., NH3
 Relative strength between fundamental and overtones ≤ 10
 Overtone bands are less forbidden
 Exception – Fermi resonance:
Accidental degeneracies (i.e., near resonances) can strengthen weak processes.
Two vibrational modes strongly coupled by radiative and collisional exchanges.
E.g., 2ν2 CO2 (i.e. 2 x 667 cm-1 = 1334 cm-1) ≈ ν1, CO2

24
 4.4. Rovibrational spectra of
polyatomic molecules
 Linear polyatomic molecules
(limit consideration to fundamental transitions)
Energy: T v i , J   G v i   F J 
 Case I: Parallel bands (symmetric and asymmetric stretch)
J'=J"+1
Selection Rule: v i  1 v'=1 J'= J"
J  1 J'= J"-1

( R and P branches) P R
v j  0, j  i J"+1
v"=0
J"

Transition Probabilities
Absorption Spectrum: P & R branches only Null Gap
R(2)
P branch R branch
Example: HCN(ν1, ν3)
R(0)   o
P(1) 2B
 Note: No ν1 parallel band for CO2
-8 -6 -4 -2 0 2 4 6
25
 4.4. Rovibrational spectra of
polyatomic molecules
 Linear polyatomic molecules
 Case I: Parallel band

= 1
Anti-symmetric
Stretching

Per cent Transmission

Vibration
Energy

= 0

_ _
𝑣 𝑐𝑚 1
_ Example-2: A parallel band (3) of the linear molecule CO2
𝑣
26
 4.4. Rovibrational spectra of
polyatomic molecules
 Linear polyatomic molecules
(limit consideration to fundamental transitions)
Energy: T v i , J   G v i   F J 
 Case II: Perpendicular bands
J'=J"+1
Selection Rule: v i  1 v'=1 J'= J"
J  1,0 J'= J"-1
(
R
,
P
a
n
d
Q
b
r
a
n
c
h
e
s
)
P Q R
v j  0, j  i J"+1
v"=0
1. If B'=B", all Q branch lines occur at J"
the same frequency
 
0
 Transition Probabilities Q branch
2. If B'≠B", Q J "  0  B' B"J "  J "1 P branch R branch
Q branch “degrades” to lower
frequencies (i.e., to the “red” in   o
wavelength) 2B
-6 -4 -2 0 2 4 6
27
 4.4. Rovibrational spectra of
polyatomic molecules
 Linear polyatomic molecules
 Case II: Perpendicular bands

Example:
Spectrum of the 2 bending mode of
HCN, showing the PQR structure

← impurity

620 660 _700 _1

740 780
𝑣 𝑐𝑚
28
 4.4. Rovibrational spectra of
polyatomic molecules
 Symmetric top molecules (e.g., CH3F, BCl3)
Recall: K – quantum number for angular momentum around axis A
Energy: T v i , J , K   G v i   F  J , K 
 v i  1 / 2 ei  ei xei v i  1 / 2   BJ  J  1   A  B K 2
2

 Case I: Parallel bands

Tripod-like
Selection Rule: v i  1
J  1,0 ( P, Q, R branches)
K  0
1. 2J+1 values of K (K=J, J-1, …, 0, …, -J)
2. Intensity of Q branch is a function of (IA/IB)
3. As (IA/IB) → 0
B symmetric top → linear molecule
strength of Q branch → 0
C

Planar 29
 4.4. Rovibrational spectra of
polyatomic molecules
 Symmetric top molecules (e.g., CH3F, BCl3)
 Case I: Parallel bands

 Note:
1. Splitting in P and R branch
due to a difference in (A-B) in
upper and lower vib. levels
2. Splitting in Q branch due to
difference in B in upper and
lower vib. levels
3. For K=0, spectrum reduces to
that of linear molecules, no Q
branch
4. K cannot exceed J

Resolved components of a parallel band showing

contributions from each of the K levels of the v=0 state
30
 4.4. Rovibrational spectra of
polyatomic molecules
 Symmetric top molecules
 Case I: Parallel bands
Per cent Transmission

R-branch P-branch
Q-branch

1340 1330 1320 1310 1300 _ 1290 1280 1270 1260

𝑣 𝑐𝑚 1
Example-1: A parallel absorption band of the symmetric top molecule CH3Br. The P
branch is partly resolved, while only the contours of the R and Q branches is obtained
31
 4.4. Rovibrational spectra of
polyatomic molecules
 Symmetric top molecules
 Case I: Parallel bands
Absorbance

1200 1225 1250 1275 1300

_1
𝑣 𝑐𝑚

Example-2: The parallel stretching vibration, centered at 1251 cm-1, of the

symmetric top molecule CH3I, showing the typical PQR contour.
32
 4.4. Rovibrational spectra of
polyatomic molecules
 Symmetric top molecules (e.g., CH3F, BCl3)
 Case II: Perpendicular bands

Selection Rule: v i  1
J  1,0 ( P, Q, R branches)
K  1

R Branch: J  1, K  1
 R  o  2 B J  1   A  B 1  2 K 

P Branch: J  1, K  1
 P  o  2 BJ   A  B 1  2 K 

Q Branch: J  0, K  1
 Q  o   A  B 1  2 K 

 Note: Two sets of R, P and Q branches for each lower state value of K
33
 4.4. Rovibrational spectra of
polyatomic molecules
 Symmetric top molecules (e.g., CH3F, BCl3)
 Case II: Perpendicular bands

◄ Energy levels of a symmetric top molecule

showing transitions that are allowed for a
perpendicular band

▼ Resulting spectrum, components of a perpendicular

band showing the contributions from each K levels
of the v=0 state

𝑣 𝑣0
34
 4.4. Rovibrational spectra of
polyatomic molecules
 Symmetric top molecules
 Case II: Perpendicular bands
Per cent Transmission

 Note: Spacing of
the Q branch lines in a
perpendicular band
can be identified with
2(A-B), and hence are
observable if A-B is
large enough

_
𝑣 𝑐𝑚 1
Example: The Q-branch of a perpendicular band, for the symmetric top
molecule CH3Cl
35
Next: Quantitative Emission/Absorption

 Spectral Absorptivity
 Eqn. of Radiative Transfer
 Einstein Coefficients/Theory
 Radiative Lifetime, Line Strength