Lecture 2: Rotational and Vibrational Spectra

1. Light-matter interaction
2. Rigid-rotor model for diatomic
molecule
3. Non-rigid rotation
4. Vibration-rotation for diatomics
 1. Light-matter interaction
 Possibilities of interaction
 Permanent electric dipole moment
 Rotation and vibration produce oscillating dipole (Emission/Absorption)
H2O HCl Energy
∆E Absorption
 = qd
Emission
What if
Homonuclear?
 Induced polarization  Elastic scattering
(Raman scattering) (Rayleigh scattering)
Virtual State

vs
s <
m or as

Inelastic scattering as >

2
 1. Light-matter interaction
 Elements of spectra: • Line position () is determined by
difference between energy levels
 Line position • What determines the energy levels?
 Line strength • Quantum Mechanics!
 Line shapes
Rotation: Microwave Region (∆J)
 Internal Energy:
Electric dipole moment:    qi r i
Eint = Eelec(n)+Evib ()+ Erot(J) i
μ +

Trot
E
Erot
Evib C
∆E μx vs
1/ν
O μx

Eelec Are some molecules Time

“Microwave inactive”? YES, e.g., H2, Cl2, CO2
3
 1. Light-matter interaction
 Elements of spectra:
 Line position
 Line strength Rotation: Microwave Region (∆J)
 Line shapes Vibration: Infrared Region (∆v, J)
 Internal Energy :
μ
Eint = Eelec(n)+Evib ()+ Erot(J)

Erot δ+ μ
t = vs
Evib C x

∆E μx
O δ-

Heteronuclear case is IR-active

Eelec Are some vibrations “Infra-red inactive”?
Yes, e.g., symmetric stretch of CO2 4
 1. Light-matter interaction
 Summary

Eint = Eelec(n)+Evib ()+ Erot(J) ∆Erot < ∆Evib < ∆Eelec

 Energy levels are discrete

 Optically allowed transitions may occur
only in certain cases
Erot  Absorption/emission spectra are discrete
Evib
∆E
Current interest
Rotation Rigid Rotor Non-rigid Rotor
Eelec Vibration Simple Harmonic Anharmonic
Oscillator Oscillator

5
 2. Rigid-Rotor model of diatomic
molecule
 Rigid Rotor
Axes of rotation

m1 m2
+ - ~ 10-13cm
r1 r2
C: r1m1 = r2m2
Center of mass C
r1+r2 = re ~ 10-8cm

Assume:
 Point masses (dnucleus ~ 10-13cm, re ~ 10-8cm)
 re = const. (“rigid rotor”)

Relax this later

6
 2. Rigid-Rotor model of diatomic
molecule
 Classical Mechanics  Quantum Mechanics
 Moment of Inertia
Value of ωrot is quantized
I   mi ri  r
2 2

Irot  J  J  1  h / 2 
e
mm
  1 2  reduced mass
m1  m2
Rot. quantum number = 0,1,2,…
2-body problem changed Erot is quantized!
to single point mass
 Rotational Energy
h2
1 2
Erot  Irot 
1
Irot   J J  1  J J  1 2
2 1 2

2 2I 2I 8 I
Convention is to denote rot. energy as F(J), cm-1
Erot  h 
F  J , cm 1   J    2  J  J  1  BJ  J  1
hc  8 Ic 
hc Erot
E , J  h   hc  J  So energy, cm-1 = (energy, J)/hc
 hc
7
 2. Rigid-Rotor model of diatomic
molecule
 Absorption spectrum
d 2 2m
Schrödinger’s Equation: 2
 2 E  U  x   x   0
dx 
 Wave function
Transition probability   m  n d  J  1   Complex conjugate


 Dipole moment

Selection Rules for rotational transitions

’ (upper) ” (lower)
↓ ↓
∆J = J’ – J” = +1

Recall: F  J   BJ  J  1

e.g.,  J 1 J 0  F  J  1  F  J  0   2 B  0  2 B

8
 2. Rigid-Rotor model of diatomic
molecule
 Absorption spectrum

Remember that: F  J   BJ  J  1

E.g.,  J 1 J 0  F  J  1  F  J  0   2 B  0  2 B
12B 3
J F 1st diff = ν 2nd diff = spacing
0 0 6B
2B
1 2B 2B 2
4B Lines every 6B
2 6B 2B
6B 2B! 4B
3 12B 2B
8B 2B 1
4 20B 2B
F=0 J=0

In general:  J 1 J   J ' J "  B  J "1 J "2   BJ "  J "1

 J ' J " , cm 1  2 BJ "1 Let’s look at absorption spectrum

9
 2. Rigid-Rotor model of diatomic
molecule
 Absorption spectrum
Recall: F J   BJ  J  1
E.g.,  J 1 J 0  F  J  1  F  J  0  2 B  0  2 B
12B 3 1.0

Heteronuclear
6B molecules only!
Tλ λJ”=0~2.5mm
6B 2 νrot for J=0→1~1011Hz (frequencies of rotation)

4B
2B 1 0.0
2B 0 1 2 3 4 5 6 7 ν/2B=J”+1
F=0 J=0
J” 0 1 2 3 4 5 6
 Note:
1. Uniform spacing (easy to identify/interpret)
2. BCO~2cm-1 λJ”=0 = 1/ν = 1/4cm = 2.5mm (microwave/mm waves)
 rot,J=1 = c/λ = 3x1010/.25 Hz = 1.2x1011Hz (microwave)
10
 2. Rigid-Rotor model of diatomic
molecule
 Usefulness of rotational spectra

Measured spectra Physical characteristics of molecule

Line spacing h
=2B
B
8 Ic
2 I  re
2
re Accurately!

Example: CO

B = 1.92118 cm-1 → rCO = 1.128227 Å

10-6 Å = 10-16 m

11
 2. Rigid-Rotor model of diatomic
molecule
 Intensities of spectral lines
Equal probability assumption (crude but useful)
 Abs. (or emiss.) probability per molecule, is (crudely) independent of J
 Abs. (or emiss.) spectrum varies w/ J like Boltzmann distribution
Degeneracy is a QM result associated w/ possible
directions of Angular Momentum vector
N J 2 J  1 exp E J / kT 
 
2 J  1 exp  r J J  1 / T 
Recall:
N Qrot T / r
E J hcF  J   hc 
    BJ  J  1   r J  J  1
k k  k 
1 kT 1 T
Partition function: rot
Q  
 hcB  r
Symmetric no. (ways of rotating to achieve same
orientation) = 1 for microwave active
 hc 
Define rotational T:  r K     B
CO: σ=1 → microwave active!
N2: σ=2 → microwave inactive!
 k  12
 2. Rigid-Rotor model of diatomic
molecule
 Intensities of spectral lines

Rotational Characteristic Temperature:  r K     B

hc
 k 
Species θrot [K]
O2 2.1
hc
N2 2.9  1.44 K / cm 1
k
NO 2.5
Cl2 0.351

N J 2 J  1 exp  r J  J  1 / T 

N T / r
Strongest peak: occurs where the population is at a local maximum
d N J / N 
0 J max  T / 2 rot   1 / 2  f T /  rot 
1/ 2

dJ

13
 2. Rigid-Rotor model of diatomic
molecule
 Effect of isotopic substitution
h
Recall: B 
8 2 Ic
Changes in nuclear mass (neutrons) do not change r0
→ r depends on binding forces, associated w/ charged particles
→ Can determine mass from B

Therefore, for example:

 
B 12C 16O 1.92118
  m13 C  13.0007
13 16

B C O 1.83669
m12C  12.00
Agrees to 0.02% of
other determinations
14
 3. Non-Rigid Rotation
Effects shrink line spacings/energies
Two effects; follows from B  1 / r
2


 Vibrational stretching r(v)

v↑ r↑ B↓
 Centrifugal distortion r(J)
J↑ r↑ B↓

Result: Fv  J   Bv J  J  1  Dv J 2  J  1
2
Centrifugal distribution constant
 J ' J ",v  2 Bv J "1  4 Dv J "13
4B3
Notes: 1. D is small; where D   B
 2
e
since,  D   B
2
 1 .7 
2

   4   4   3  10
6

 B  NO  e   1900 
→ D/B smaller for “stiff/hi-freq” bonds

15
 3. Non-Rigid Rotation
4B3
 Notes: 1. D is small; D   B
 2
e
2
e.g.,  D   B  1 .7 
2

      4
4   3 10
6

 B  NO  e   1900 
→ D/B smaller for “stiff/hi-freq” bonds
2. v dependence is given by B v  Be   e v  1 / 2 
D v  De   e v  1 / 2 
E.g., NO
Aside:
Be  1.7046cm 1
 e / Be ~ 0.01 8e xe 5 e  e2e
 e / De     1
 e / De ~ 0.001

 e  0.0178 e Be 24 Be3

De  5.8  10 6 2 1/ 2   Herzberg, Vol. I
 e  0.0014 De ~ 8  10 9 cm 1 e denotes “evaluated at equilibrium
e  1904.03 2 1/ 2 ;1903.68 2  3 / 2  inter-nuclear separation” re
e xe  13.97cm 1
16
 4. Vibration-Rotation Spectra (IR)

1. Diatomic Molecules
 Simple Harmonic Oscillator (SHO)
 Anharmonic Oscillator (AHO)
2. Vibration-Rotation spectra – Simple model
 R-branch / P-branch
 Absorption spectrum
3. Vibration-Rotation spectra – Improved model
Vibration-Rotation spectrum of CO
4. Combustion Gas Spectra (from FTIR)

17
 4.1. Diatomic Molecules
 Simple Harmonic Oscillator (SHO)

∆/2 rmin

m1 m2

re
Equilibrium position (balance
Molecule at instance of greatest
between attractive + repulsive
compression forces – min energy position

As usual, we begin w. classical mechanics

+ incorporate QM only as needed

18
 4.1. Diatomic Molecules
 Simple Harmonic Oscillator (SHO)
Classical mechanics
 Force  k s r  re  - Linear force law / Hooke’s law
1
 Fundamental Freq.  vib  ks /  e , cm 1   / c
2
U  k r  re 
1
 Potential Energy 2

2
Parabola centered at distance
Quantum mechanics of min. potential energy
 v = vib. quantum no.
= 0,1,2,3,… real

 Vibration energy G=U/hc = diss.

G v , cm 1  e  v vib / c v  1 / 2  energy

 Selection Rules: Equal energy

spacing
v  v' v"  1 only! Zero energy

19
 4.1. Diatomic Molecules
 Anharmonic Oscillator (AHO)
SHO AHO
G v , cm 1  e v  1 / 2  G v , cm 1  e v  1 / 2  e xe v  1 / 2   ...  H .O.T .
2

Decreases energy spacing 1st anharmonic correction

 10  G 1  G  0 
“Fundamental” Band
∆ν=+1  e 1  2 xe 
real (e.g., 1←0,2←1)
 21  e 1  4 xe 

1st Overtone
∆ν=+2
(e.g., 2←0,3←1)
 20  2e 1  3 xe 

2nd Overtone
∆ν=+3
(e.g., 3←0,4←1)
 30  3e 1  4 xe 

In addition, breakdown in selection rules

20
 4.1. Diatomic Molecules
 Vibrational Partition Function
1
   hce    hce 
Qvib  1  exp  exp 
  kT    2 kT 
The same zero energy must
Choose reference (zero) energy at v=0, so G v   e v be used in specifying
1 molecular energies Ei for
   hce  level i and in evaluating the
Qvib  1  exp 
  kT  associated partition function

 Vibrational Temperature
 hc 
 vib K    e Species θvib [K] θrot [K]
 
k
N vib g vib exp v vib / T  O2 2270 2.1

N Qvib N2 3390 2.9
 v      NO 2740 2.5
 exp  vib  1  exp  vib 
 T   T  Cl2 808 0.351
where g vib  1

21
 4.1. Diatomic Molecules
 Some typical values (Banwell, p.63, Table 3.1)

Molecular Vibration ωe Anharmonicity Force constant ks Internuclear Dissociation

Gas Weight [cm-1] constant xe [dynes/cm] distance re [Å] energy Deq [eV]

CO 28 2170 0.006 19 x 105 1.13 11.6

NO 30 1904 0.007 16 x 105 1.15 6.5
H2† 2 4395 0.027 16 x 105 1.15 6.5
Br2† 160 320 0.003 2.5 x 105 2.28 1.8

 † Not IR-active, use Raman spectroscopy!

 e  k /  ←   m / 2 for homonuclear molecules
 De  e / 4 xe ← large k, large D
 Weak, long bond → loose spring constant → low frequency

22
 4.1. Diatomic Molecules
 Some useful conversions
 Energy 1 cal  4.1868 J
1 cm -1  2.8575 cal/mole
1 eV  8065.54 cm 1  23.0605 kcal/mole  1.60219  10 19 J
 Force 1 N  105 dynes
o
 Length 1 A  0.1 nm

How many HO levels? (Consider CO)

Do  256 kcal

N  no. of HO levels
256 kcal/mole
  41
 2.86 cal/mole cm 1
 2170 cm 1

Actual number is ?GREATER

as AHO shrinks level spacing

23
 4.2. Vib-Rot spectra – simple model
 Born-Oppenheimer Approximation
 Vibration and Rotation are regarded as independent
→ Vibrating rigid rotor
Energy: T v, J   RR  SHO  F  J   G v 
∆J = J' - J"
 BJ  J  1  e v  1 / 2 
Selection Rules: v  1 Two Branches: P (∆J = -1)
J  1 R (∆J = +1)
Line Positions:   T 'T "  T v' , J '  T v" , J " Aside: Nomenclature for “branches”
 Branch O P Q R S
 ∆J -2 -1 0 +1 +2
J'=J"+1
v'=1 J'= J"
Transition Probabilities

Null Gap
J'= J"-1 R(2)
P branch R branch
P R
R(0)
J"+1 P(1)
v"=0   o
J" 2B
-8 -6 -4 -2 0 2 4 6
24
 4.2. Vib-Rot spectra – simple model
 R-branch
 R  J ", cm 1  G v'  G v"  B  J "1 J "2   BJ "  J "1

o  v o = Rotationless transition wavenumber

 e (SHO)
 e 1  2 xe  (AHO,1  0)
 e 1  4 xe  (AHO,2  1)
 ...
R  J "  0  2 B  J "1 Note: spacing = 2B, same as RR spectra

J'=J"+1
 P-branch v'=1 J'= J"
J'= J"-1
 P  J "  0  2 BJ " Note: ωo = f(v") for AHO
P R
J"+1
v"=0
_ 8 BkT J"
 P-R Branch peak separation  
hc
Larger energy
25
 4.2. Vib-Rot spectra – simple model
 Absorption spectrum (for molecule in v" = 0)

Width, shape depends on instrument,

experimental conditions
Transition Probabilities

Null Gap
R(2)
P branch R branch Line
(sum of all lines is a “band”)
R(0)
P(1)
  o
-8 -6 -4 -2 0 2 4 6 2B

 Height of line ∝ amount of absorption ∝ NJ/N

 “Equal probability” approximation – independent of J (as with RR)

What if we remove RR limit? → Improved treatment

26
 4.3. Vib-Rot spectra – improved model
 Breakdown of Born-Oppenheimer Approximation
 Allows non-rigid rotation, anharmonic vibration, vib-rot interaction
T v, J   G v   F v, J  B(v)
 e v  1 / 2   e xe v  1 / 2   Bv J  J  1  Dv J 2 J  1
2 2

SHO Anharm. corr. RR(v) Cent. dist. term

 R-branch R v" , J "  o v"  2 Bv '3Bv ' Bv "J "Bv ' Bv "J "2
 P-branch P v" , J "  o v"  Bv ' Bv "J " Bv ' Bv "J "2

Bv  Be   e v  1 / 2  Bv '  Be ' e v'1 / 2

Bv "  Be " e v"1 / 2 Bv '  Bv "
Bv ' Bv "   e  0 Spacing ↑ on P side, ↓ on R side
Transition Probabilities

Null Gap
R(2)
P branch R branch
R(0)
P(1)   o
-8 -6 -4 -2 0 2 4 6 2B 27
 4.3. Vib-Rot spectra – improved model
 Bandhead
Transition Probabilities
Null Gap
R(2)
P branch R branch
R(0)
P(1)   o
2B
-8 -6 -4 -2 0 2 4 6
P branch J" R branch
4
Bandhead
3
2
1
  o
-4 -3 -2 -1 0 1 2 3 4 2B
dRJ  2 B' e B
 3B' B"  2B ' B"J "  0 J "bandhead  
dJ     2 e e
2 B ' 
e  e
Increasing Decreasing
spacing spacing
B 1.9
E.g., CO   106 → not often observed
e 0.018
28
 4.3. Vib-Rot spectra – improved model
 Finding key parameters: Be, αe, ωe, xe
 1st Approach:
Use measured band origin data for the fundamental and first
overtone, i.e., ΔG1←0, ΔG2←0, to get ωe, xe
G10  G 1  G 0   e 1  2 xe 
e , xe
G20  G 2   G 0   2e 1  3 xe 

 2nd Approach:
Fit rotational transitions to the line spacing equation to get Be and α
  o  B ' B"m  B' B"m 2
m  J  1 in R - branch
m   J in P - branch

B '  Be   e V
v ' 1/ 2 
B', B" Be, α
B "  Be   e V
v " 1/ 2 

29
 4.3. Vib-Rot spectra – improved model
 Finding key parameters: Be, αe, ωe, xe
 3rd Approach: Use the “method of common states”

v' J'= J" ← Common upper-state

J'= J"-1 In general F  J   BJ  J  1
P(J+1) R(J-1) E  F J  1  F J  1
v" J"+1  R J  1  P J  1
∆E J"  B" J  1 J  2   B"  J  1J
J"- 1  E  B" 4 J  2  B"

v' J'=J"+1 Be , 
E  F  J  1  F J  1
∆E J'= J"
 B ' J  1J  2   B ' J  1J
J'= J"-1
 E  B ' 4 J  2  B'
P(J) R(J)
v" J"+1
J" ← Common lower-state
30
 4.3. Vib-Rot spectra – improved model
 Isotopic effects
1 1
B  → Line spacing changes as μ changes
I 
ks 1
e   → Band origin changes as μ changes
 

1st Example: CO Isotope 13C16O

 B13 C16O
 1.046  B13 C16O 
13
C 16O
 12
C 16O
1.046
 2 B   0.046  3.88  0.17cm 1
e
 e 13 C16O 
13
C 16O

1.046
e  0.046  2200 / 2  50cm 1

31
 4.3. Vib-Rot spectra – improved model
 Isotopic effects

CO fundamental band
Note evidence of 1.1%
natural abundance of 13C

32
 4.3. Vib-Rot spectra – improved model
 Isotopic effects
1 1
B  → Line spacing changes as μ changes
I 
ks 1
e   → Band origin changes as μ changes
 

2nd Example: HCl Isotope H35Cl and H37Cl

 H Cl   3H Cl 
35 37

37.1 / 38
 37 / 35  35.1 / 36
 1.0015

Shift in ωe is .00075ωe=2.2cm-1 → Small!

33
 4.3. Vib-Rot spectra – improved model
 Isotopic effects

HCl fundamental band

Note isotropic splitting due to H35Cl and H37Cl

34
 4.3. Vib-Rot spectra – improved model
 Hot bands
When are hot bands (bands involving excited states) important?
 v 
g exp  v 
Nv
  T   exp  v v  1  exp   v 
   
N Qvib  T   T 
N1  e 10  0 @ 300 K
E.g.  v ,CO  3000 K 
 
N e 1 1  e 1  0.23 @ 3000 K
“Hot bands” become important when temperature is comparable to the
characteristic vibrational temperature

Gas  01 cm 1  N1 / N 0  e  hc / kT

300K 1000K
H2 4160.2 2.16 x 10-9 2.51 x 10-3
HCl 2885.9 9.77 x 10-7 1.57 x 10-2
N2 2330.7 1.40 x 10-5 3.50 x 10-2
CO 2143.2 3.43 x 10-4 4.58 x 10-2
O2 1556.4 5.74 x 10-4 1.07 x 10-1
S2 721.6 3.14 x 10-2 3.54 x 10-1
Cl2 566.9 6.92 x 10-2 4.49 x 10-1
I2 213.1 2.60 x 10-1 7.36 x 10-1

35
 4.3. Vib-Rot spectra – improved model
 Examples of intensity distribution within the rotation-vibration band

B = 10.44cm-1 (HCl) B = 2cm-1 (CO)

36
 4.4. Absorption Spectra for Combustion Gases
 TDL Sensors Provide Access to a Wide Range of Combustion
Species/Applications

 Small species such as NO,

CO, CO2, and H2O have
discrete rotational transitions
in the vibrational bands

 Larger molecules, e.g.,

hydrocarbon fuels, have
blended spectral features

37
Next: Diatomic Molecular Spectra
 Electronic (Rovibronic) Spectra (UV, Visible)