CHEM3117 (Quantum & Spectroscopy) Lecture 20 Rotation-Vibration Spectroscopy

Take home messages from last lecture:

1. Molecules with a dipole moment can absorb microwave radiation by rotating. 2. rotational motion is quantised because rotational wavefunction must have wavelength of an integer times 2
3. Linear molecule: F(J) = BJ(J+1) 4. Each energy level is 2J+1-fold degenerate

2011, Kable, Jordan, Schmidt

Lecture 20-2

Example question
Q: From the microwave spectrum below, determine the CO bond length, given that the spacing between the rotational lines is 3.86 cm-1.

10B 12B 14B 16B 18B 20B 22B

2B

2B

2B

4B

24B 26B 28B 30B 32B

6B

8B

2011, Kable, Jordan, Schmidt

Lecture 20-

Example question
Q: From the microwave spectrum below, determine the CO bond length, given that the spacing between the rotational lines is 3.86 cm-1.

F = BJ(J+1)
F=BJ2+B

F = 2BJ
dF/dJ=2BJ

F = 2B
d2F/dJ2=2B

2B = 3.86 cm-1

=>

B = 1.93 cm-1
kg m2

h 8 2cI

=> I = 1.45 x 10-46

B is in cm-1, so c must be in cm/s

I = R2 =

m1m2R 2/(m1+m2)

In S.I. units, m is in kg

R = 1.125 x 10-10 m or 1.125

2011, Kable, Jordan, Schmidt

Lecture 20-4

Today
1. Rotation-vibration spectroscopy 2. Rotational selection rules 3. Effect of temperature on intensity

2011, Kable, Jordan, Schmidt

Lecture 20-5

Vibration-rotation energy levels (for a diatomic):

Vibrational energy levels

Rotational energy levels

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Lecture 20-6

Vibration-rotation energy levels (for a diatomic):

Rotational energy levels Each vibrational state has its own set of rotational levels
2011, Kable, Jordan, Schmidt

Lecture 20-7

Jablonski diagrams:

A Jablonski diagram plots energy on the y-axis, but nothing on the x-axis. It is a simplified way to draw an energy level diagram when you don t want/need to show the potential energy function.

2011, Kable, Jordan, Schmidt

Lecture 20-8

Jablonski diagrams:
The timescales for vibrational and rotational motion are very different. Therefore we can treat each motion as happening independently of each other.
1 rotation 10 ps (10-11 s) 1 vibration 10 fs (10-14 s)

A consequence of this is that we can treat the energy of a combined state as the sum of the vibrational and rotational energies separately.

2011, Kable, Jordan, This is like the Schmidt Born-Oppenheimer

approximation.

Lecture 20-9

Vibration-rotation energy:
We can treat the vibrational and rotational energies separately: Vib:

(Harmonic oscillator)

G(v) = (v + 1 2)
F ( J ) = BJ ( J + 1)

Rot:

(Rigid rotor)

Combined:

S (v, J ) = (v + 1 2) + BJ ( J + 1)
2011, Kable,have Jordan, Schmidt You could used the

anharmonic vibrational energy here if necessary.

Lecture 20-10

Vibration-rotation selection rules:

We can treat the vibrational and rotational energies separately.
The selection rules for both vibration and rotation apply: v = 1 (harmonic oscillator) J = 1* (from ang. momentum of photon)

Are these v=0, J=0 v=0, J=8 v=1, J=9

2011, Kable, Jordan, Schmidt * Sometimes J=0 is allowed

transitions allowed? v=1, J=1 v=1, J=7 v=0, J=10

Lecture 20-11

for vib-rot spectra (see next lecture).

Allowed vib-rot transitions

Firstly, consider an absorption spectrum. This means that v = +1

J can be either +1 or -1. Let s look at these one at a time

J = +1

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Lecture 20-12

R-transitions
J = +1
The transitions are getting longer (higher energy)

These are called R transitions

the initial state

R(9) R(5) R(0)

R(9)
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R(0)
Lecture 20-13

P-transitions
J = -1
The transitions are getting shorter (lower energy)

These are called P transitions

the initial state

P(9) P(5) P(1)

P(9)
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P(1)
Lecture 20-14

Labelling a rot-vib. spectrum

1. Find the gap (explanation later) 2. Label the R-branch to higher wavenumber 3. Label the P-branch to lower wavenumber 1
R(0) P(3) P(1)

3
P(5) P(7)

R(2)

2
R(4) R(6)

HCl
2011, Kable, Jordan, Schmidt

P(9)

Lecture 20-15

R(8)

Simplified analysis
S (v, J ) = (v + 1 2) + BJ ( J + 1)
R(0) is S(1,1) S(0,0) = (1.5+2B) - (0.5+0B) = + 2B R(1) is S(1,2) S(0,1) = (1.5+6B) - (0.5+2B) = + 4B P(1) is S(1,0) S(0,1) = (1.5+0B) - (0.5+2B) = - 2B P(2) is S(1,1) S(0,2) = (1.5+2B) - (0.5+6B) = - 4B
2011, Kable, Jordan, Schmidt

S(1,1) S(0,0)

Lecture 20-16

Labelling a rot-vib. spectrum

P(1) = - 2B P(2) = - 4B P(3) = - 6B P(4) = - 8B etc 2B
P(3)

2B! Bandgap 4B
R(0) P(1)

2B!

R(0) = + 2B R(1) = + 4B R(2) = + 6B R(3) = + 8B etc 2B

R(2)

P(5)

R(4)

P(7)

R(6)

HCl

P(9)

2011, Kable, Jordan, Schmidt

Lecture 20-17

R(8)

Let s have a look at the experimental peak separations

HCl
P(3) P(2) P(1) R(0) R(1) R(2) Freq. / cm-1 2821.59 2843.63 2865.14 2906.25 2925.92 2944.99

We have 5 differences here

2B = 22.04 2B = 21.51 4B = 41.11 2B = 19.67 2B = 19.07 B = 11.02 B = 10.76 B = 10.28 B = 9.84 B = 9.54 Why are these systematically different?

Av. = 10.29 cm-1

Note that the twice as large separation between the central peaks is predicted.
2011, Kable, Jordan, Schmidt

Lecture 20-18

A closer look
The systematic difference arises from slightly different energy level spacings in the v=0 and v=1 state. B must be different in the two states. Let s re-examine the expression for the transition frequency.

F(J) = BJ(J+1) F(J) = BJ(J+1)

R(1) is S(1,2) S(0,1) = (1.5+6B) - (0.5+2B) = + 6B 2B (c.f. R(1) = + 4B previously)
S (v, J) = 2011, Kable, Jordan, Schmidt Remember: (v + 1 2) + BJ ( J + 1)

3 unknowns = 3 equations?
Lecture 20-19

A closer look
Let s analyse R(1) and P(1)
R(1) is S(1,2) S(0,1) = (1.5+6B) - (0.5+2B) = + 6B 2B P(1) is S(1,0) S(0,1) = (1.5+0B) - (0.5+2B) = 2B Subtract:
Freq. / cm-1 2821.59 2843.63 2865.14 2906.25 2925.92 2944.99

P(3) P(2) P(1) R(0) R(1) R(2)

These are just numbers in a table

R(1) P(1) = 6B

Choose any two transitions with the same lower state and you cancel all knowledge of that vib. state, leaving you with a simple problem involving the upper vib. state.
2011, Kable, Jordan, Schmidt

Lecture 20-20

A closer look
Let s analyse R(0) and P(2)
R(0) is S(1,1) S(0,0) = (1.5+2B) - (0.5) = + 2B P(2) is S(1,1) S(0,2) = (1.5+2B) - (0.5+6B) = + 2B 6B Subtract:
P(3) P(2) P(1) R(0) R(1) R(2) Freq. / cm-1 2821.59 2843.63 2865.14 2906.25 2925.92 2944.99

These are just numbers in a table

R(0) P(2) = 6B

Choose any two transitions with the same upper state and you cancel all knowledge of that vib. state, leaving you with a simple problem involving the other vib. state.
2011, Kable, Jordan, Schmidt

Lecture 20-21

Combination Differences
Reminder:
Choose any two transitions with the same lower state and you cancel all knowledge of that vib. state, leaving you with a simple problem involving the upper vib. state. Choose any two transitions with the same upper state and you cancel all knowledge of that vib. state, leaving you with a simple problem involving the other vib. state.

This procedure is called taking combination differences. It is a widely used technique in spectroscopy finding transitions with the same initial or final state to provide information about the other states.
2011, Kable, Jordan, Schmidt

Lecture 20-22

Q: An IR spectrum of HCl is shown below. i) Assign the transitions in the spectrum. (2 mks) ii) From the measurements of the spectrum in the table below, calculate the bond length of HCl in the v=0 and v=1 states. (8 mks) iii) Draw a potential energy diagram and comment about the bond lengths you have calculated above. (3 mks) iv) What is the wavenumber of the pure vibrational transition? (2 mks)
R(0)

R(2)

P(3)

P(1)

i)
P(5) P(7) P(9)

Freq. / cm-1
R(4)

P(3)
R(6)

2821.59 2843.63 2865.14 2906.25 2925.92 2944.99

Lecture 20-23

P(2)
R(8)

P(1) R(0) R(1) R(2)

2011, Kable, Jordan, Schmidt

ii) From the measurements of the spectrum in the table below, calculate the bond length of HCl in the v=0 and v=1 states. (8 mks)

Calculate B and B (this is what you need to work out R)

From previous:
R(0) P(2) = 6B 2906.25 2843.63 = 6B 62.62 = 6B B=10.44 cm-1 R(1) P(1) = 6B 2925.92 2865.14 = 6B 60.78 = 6B B=10.13 cm-1 Freq. / cm-1
R(0) P(1) R(2)

P(3)
R(4)

2821.59 2843.63 2865.14 2906.25 2925.92 2944.99

Lecture 20-24

P(5)

P(3)

P(2)
R(6)

P(7)

P(1)
R(8)

P(9)

R(0) R(1) R(2)

HCl

2011, Kable, Jordan, Schmidt

B = 10.44 cm-1

B = 10.13 cm-1

B
I = 2.679 x 10-47

h 8 2cI

B is in cm-1, so c must be in cm/s c = 3.00 x 1010 cm/s

kg m2

I = 2.761 x 10-47

kg m2

m1m2 2 I = R = m + m R 2 1
2

In S.I. units, m is in kg 1 amu = 1.67 x 10-27 kg

R = 1.28 x 10-10 m or 1.28

R = 1.30 x 10-10 m or 1.30

In this measurement, you are watching the bond get longer (weaken) as you add energy. Eventually the bond breaks.
2011, Kable, Jordan, Schmidt

Lecture 20-25

iii) Draw a potential energy diagram and comment about the bond lengths you have calculated above. (3 mks)
The bond gets longer as it vibrates more

v=15 v=10 v=5

re
2011, Kable, Jordan, Schmidt

r0

r1

R = r0= 1.28 R = r1= 1.30

r
Lecture 20-26

iv) What is the wavenumber of the pure vibrational transition? (2 mks)

The pure vibrational transition is the hypothetical transition from v=0, J=0 to v=1, J=0 (which is not observed) R(0) = + 2B
Freq. / cm-1 P(3) P(2) P(1) R(0) R(1) R(2) 2821.59 2843.63 2865.14 2906.25 2925.92

2906.25 = + 2 x 10.13

= 2906.25 20.26 = 2885.99 cm-1 You could have used any other transition to do this calculation, or do a graphical solution to get errors.
R(6) R(8)

P(3)

P(1)

R(2)

2944.99

R(0)

P(9)

P(7)

P(5)

R(4)

2011, Kable, Jordan, Schmidt

Lecture 20-27

Examine some real spectra:

Fundamental P-branch

CO
R-branch

First overtone

Second overtone

2011, Kable, Jordan, Schmidt

Lecture 20-28

Examine some real spectra:

CO

First overtone

P-branch

R-branch

Notice: R-branch lines get closer together P-branch lines get further apart
2011, Kable, Jordan, Schmidt

Lecture 20-29

Use Rot calculator.xls to explore

B = 10.44 cm-1
35 30 25 20
J

B = 10.44 cm-1

Examine the P and R transitions as B changes for constant B.

Fortrat parabolas

P branch R branch

Plotted in this way, the parabolic dependence of line position with J is apparent (Fortrat parabolas).
Fortrat parabolas

B = 10.13 cm-1
35 P branch R branch 30

15 10 5 0 2000

25

Wavenumber

2500

3000

3500

20 15 10

4000

B > B
2011, Kable, Jordan, Schmidt

5 0 2000

2200

2400

2600

2800
Wavenumber

3000

3200

3400

3600

R-branch gets closer spaced. R < R (molecule is bigger in the excited state)
Lecture 20-30

Use Rot calculator.xls to explore

B = 10.44 cm-1
35 30 25 20
J

B = 10.44 cm-1

Examine the P and R transitions as B changes for constant B.

Fortrat parabolas

P branch R branch

Plotted in this way, the parabolic dependence of line position with J is apparent (Fortrat parabolas).
Fortrat parabolas

B = 10.7 cm-1
35 30 25 20 4000 15 10 P branch R branch

15 10 5 0 2000

2500

3000
Wavenumber

3500

B < B
2011, Kable, Jordan, Schmidt

5 0 2000

2500

3000

3500

4000

4500

Wavenumber

P-branch gets closer spaced. R > R (molecule is smaller in the excited state)
Lecture 20-31

The temperature dependence of spectra

What causes this very distinctive band shape?

HCl
2011, Kable, Jordan, Schmidt

Lecture 20-32

The temperature dependence of spectra

Why does it change with temperature?

Low temp

High temp

HCl

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Lecture 20-33

What do I need to know?

- In an exam context, you need to be able to explain why a spectrum looks the way it does, how to apply the B-O approx. (as applied to the separation of vibrational and rotational motion), and do simple calculations involving energy of rotational states to get B, and hence R.

2011, Kable, Jordan, Schmidt

Lecture 20-34

Copyright notice
Some images used in these lectures are taken, with permission, from Physical Chemistry, T. Engel and P. Reid, (Pearson, Sydney, 2006); denoted ER throughout the lectures and other sources as indicated, in accordance with the Australian copyright regulations.

2011, Kable, Jordan, Schmidt

Lecture 20-35