1

CHEM 3364 HCl/DCl Data Manipulation

Theory

Rotational Spectroscopy

The quantum mechanical model for rotational spectroscopy is the particle-on-a-sphere

(usually referred to as the rigid rotor model in the context of rotational spectroscopy).

Consider a diatomic molecule with a fixed bond length.

r1 r2
m1 m2

center of mass

Rotation of the molecule depends on its moment of inertia, I.

I α = ∑ m i ri,2α
i
1
- For homonuclear diatomic I = m r 2 where r = r1 + r2
2
- For heteronuclear diatomic I = µ r 2 where µ is the reduced mass

Recall the energy of the rigid rotor.

h2
E= J ( J+ 1) where J is the total angular momentum and J = 0, 1, 2, 3, …
2I

E ( J)
Define a general spectroscopic term as F ( J ) =
hc
-1
- Units of spectroscopic terms are usually cm , i.e., wavenumbers.
- Why bother?
- Used historically by spectroscopists to relate units of theoretical values to the units
of the spectra.
- No substantial difference between energies (in Joules) and terms (in inverse
centimeters).

h
The rotational constant, B, is defined as B =
4π c I
Thus the spectroscopic term with the rotational constant has the simple form
F ( J ) = B J ( J+ 1)

The selection rules for transitions in the rigid rotor are ∆J = ±1

 2

When ∆J = +1 , the spectral lines are labeled the R-branch.

F ( J + 1) − F ( J ) = B ( J + 1)( J + 2 ) − B J ( J + 1) = B ( J 2 + 3J + 2) − B ( J 2 + J ) = 2B ( J + 1)

When ∆J = −1 , the spectral lines are labeled the P-branch.

F ( J −1) − F ( J ) = B ( J − 1) J − B J ( J + 1) = B ( J 2 − J ) − B ( J 2 + J ) = −2 B J

***Note the very important idea that a single line on a spectrum comes from the difference
of two term levels (energy levels) in the molecule.***

Rotovibrational Spectroscopy

Spectroscopic Term
2
 1  1  1
T ( ν , J ) = ν% e  ν +  − x eν% e  ν +  + B J ( J + 1) − DJ 2 (J + 1) − αe  ν +  J ( J+ 1)
2
(1)
 2  2  2

Pure Vibration (harmonic oscillator)

 1 1 k
ν% e  ν +  ν% e – fundamental frequency ν% e =
 2 2 πc µ

Pure Rotation (rigid rotor)

h
B J ( J+ 1) B – rotational constant B=
4 πcI

Anharmonic Oscillation
h ν% e
2
 1
− x e ν% e  ν +  x e – anharmonic constant xe =
 2 D ec

Centrifugal Distortion
4B3
− D J 2 (J + 1)
2
D – centrifugal distortion constant D0 =
cν% e2
- As a molecule rotates faster, the centrifugal force causes the bonds to stretch, thus
changing the moment of inertia of the molecule, thus changing its energy.

Harmonic Oscillator Interaction

1

 1  χe B  6B2 3 2
−α e  ν +  J ( J + 1) α e – vibration-rotation interaction constant αe = 6 2 
−
 2  ν% e c  ν% e c

- As the molecule vibrates, the moment of inertia is constantly changing.

- At low J and low ν, the vibration does not affect the rotational energy levels since the
rotation is slow compared to the vibrational motion. Thus as a molecule rotates, the
bond lengths oscillate several times in the course of one rotation. Therefore, using an
average bond length in the moment of inertia expression is appropriate.
 3

Selection Rules

∆ν = ± 1 ∆J = ±1
- For the region of the infrared spectrum that we are considering, ν = 1 ← ν = 0

When ∆J = +1 , portion of spectrum is called R-branch.

T ( ν = 1,J + 1) − T ( ν = 0,J )
(2)
= ν% e − 2x e ν% e + ( 2B − 3α e − 4D ) + ( 2B − 4α e − 12D ) J − ( α e + 12D ) J 2 − 4 D J3

When ∆J = −1 , portion of spectrum is called P-branch.

T ( ν = 1,J ) − T ( ν = 0,J − 1) = ν% e − 2x e ν% e + ( 2B − 2α e ) J − α e J 2 − 4 D J3 (3)

The lines of the R-branch and P-branch have a much simpler form if the following
substitutions are made for the J quantum number.
- For the R branch, let m = J +1 i.e., J = m − 1
- For the P branch, let m = J
When this substitution is made, the differences of terms that describe the spectral lines have
a single form for both the R and P-branches.

T ( ν = 1,m) − T ( ν = 0,m − 1) = ν% e − 2x e ν% e + ( 2B − 2α e ) m − α e m2 − 4Dm3 (4)

Background Assignment

Put the following in appendices of your report.

1.) Prove Equations (2) and (3) above using Equation (1)
2.) Prove Equation (4) for the R branch.

Extracting Data
Once the wavenumbers of the spectral lines are known (from the Winfirst program on the
FTIR), the lines need to be sorted since the resolution of the spectrometer allows for the
determination of four different spectra. (Two from each run.) The HCl spectrum yields the
H35 Cl spectrum and the H37 Cl. Also the DCl spectrum yields D35 Cl and D37 Cl spectra.

1. Once the lines are sorted, quantum numbers, m, must be assigned to all of the lines.
- Refer to the Shoemaker text, for a clear illustration of how to make the assignments.

The wavenumbers and their associated quantum numbers will be entered into a spreadsheet
program (Excel).

2. Using Excel, these points are to be fitted to a cubic polynomial with the quantum
number as the independent variable. (Use –m for the P branch.)
 4

3. By comparing the fitted equation to Equation (4), the following spectroscopic constants
can be found.
ν% e − 2x e ν% e , B, α e , D
The above values to be found for each spectrum, H35 Cl, H37 Cl, D35 Cl and D37 Cl.

4. Compare these values to experimental values. Cite primary sources for experimental
values.

Use of the Spectroscopic Constants

5. Once the spectroscopic constant B has been found, use it to calculate the bond distance
of each molecule.
h h
B= =
4 πcI 4πcµr 2

6. Confirm that our calculated rotational constants are internally consistent by calculating
the following ratios that exploit the spectroscopic differences of isotopomers.

BH35 Cl µ D35 Cl rD235 Cl BH35 Cl µ D35 Cl

= Assume rHCl = rDCl ⇒ =
BD35 Cl µ r 2
H 35 Cl H35 Cl
BD35 Cl µ H35 Cl

Use CRC to calculate reduced masses.

7. Note also that we can compare the 35 Cl and 37 Cl isotopomers.

8. Once ν% 0 = ν% e − 2x e ν% e is found, use it to calculate the force constant of the bond.

Let ν% 0 = ν% e − 2x e ν% e

1 k
Then, recall that ν% 0 =
2π c µ

9. The calculated anharmonic vibrational frequency also need to checked for internally
consistency.

ν% 0HCl µ DCl
=
ν% 0DCl µ HCl

10. Again we can make comparisons for both the 35 Cl and 37 Cl isotopomers.