1

CHEM 3364 N2 Data Manipulation

Introduction

Anharmonicity and Vibronic Spectra

Compare harmonic oscillator potential to anharmonic oscillator.

harmonic oscillator

De - dissociation energy

anharmonic oscillator

Harmonic Oscillator Anharmonic Oscillator

1 1
V = kx 2 V = kx 2 − αx 3 + βx 4 +L
2 2
 1  1  1
2
 1
3
E = hcν% e  ν +  E = hcν% e  ν +  + hcχe ν% e  ν +  + hcy eν% e  ν +  + L (1)
 2  2  2  2

Vibronic Spectra

Transitions occur between different electronic states and different vibrational states.

E
Πu
3

Two different electronic states have

two different potential energy curves.
Πg
3

R
Selection Rules

- Roughly, vibronic spectra have no selection rules

- We will learn about the selection rules of vibronic spectra in lecture.
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Vibronic Terms

T = Telectronic + G vibrational + Frotational

T ( e l′, ν′ , J′ ) − T ( el′′, ν′′, J′′ )

= Tel′ − Tel′′ + G vib ( ν ′) − Gvib ( ν′′ ) + Frot ( J′ ) − Frot ( J′′ )
= Tel′ − Tel′′ + G vib ( ν ′) − G vib ( ν′′ )

- We won’t consider differences in rotational energies since the spectral lines are too
close together to be resolved.

2 3
 1  1  1
T ( e l′, ν′ ) − T ( el′′, ν′′ ) = ν% = ν% el + ν% e′  ν′ +  + χ e′ν% e′  ν ′ +  + ye′ν% e′  ν ′ + 
 2  2  2
(2)
  1  1
2
 1 
3

−  ν% e′′  ν′′ +  + χ e′′ν% e′′  ν′′ +  + ye′′ν% e′′  ν ′′ +  

  2  2  2  

1 ′
ν% = ν% el +
2 ( 1
4) ( ) ( 1
ν% e − ν% e′′ − χ e′ %νe′ − χe′′ν% e′′ + ye′ν% e′ − ye′′ν% e′′
8 )
+  ν% e′ − χ e′ %νe′ + y e′ν% e′  ν ′ − ν% e′′ − χe′′ν% e′′ + ye′′ν% e′′  ν ′′
3 3
(3)
 4   4 
 3   3 
−  χe′ %νe′ − ye′ν% e′  ( ν′ ) +  χe′′ν% e′′ − y e′′ν% e′′  ( ν′′ ) + ye′ν% e′ (ν ′ ) − ye′′ν% e′′ ( ν ′′)
2 2 3 3

 2   2 
This equation takes a simpler form if we make the following definitions.
1
2
( ) (1
4
) ( 1
ν% 00 = ν% el + ν% e′ − ν% e′′ − χe′ν% e′ − χe′′ν% e′′ + y e′ν% e′ − y e′′ν% e′′
8
)
3
ν% 0 = ν% e − χe ν% e + y e ν% e
4
3
χ0 ν% 0 = χe %νe − ye ν% e
2
y0 ν% 0 = y e ν% e

The potential energy curves of the electronic states in nitrogen that we are considering are
similar. This similarity makes ν% ′0 = ν% ′′0

Thus our spectral lines are described by the equation,

( 2 2
) (
ν% = ν% 00 + ν% 0 ( ν′ − ν′′ ) − ν% 0 χ0′ ( ν′) − χ0′′ ( ν′′ ) + ν% 0 y0′ ( ν′ ) − y0′′ ( ν′′)
3 3
)
If we could assign vibrational quantum numbers , ν′ and ν″ to each spectral line, we could
take the differences of the spectral line energies to ν% 0 , χe, ye for each electronic state.
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Deslandres Table

We need a way to find energy differences with the same electronic state rather than
between two different electronic states.

Consider the following energy level diagram.

5
4
ν′ 3
πu
3
2
1
0

5
4
3
πg
3
2
1
0

Differences in energies yields difference Arc-spark

between ν′ = 0 and ν′ = 1 states. Spectrum

Differences in energies yields difference

between ν′′ = 2 and ν′′ = 3 states.

**Taking the differences of appropriate lines in the spectrum yields information about a
single electronic state!**
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To sort all of these differences, we use a Deslandres table.

1. To start Deslandres table, we need to identify each band with the appropriate quantum
numbers, ν′ and ν″.
- The ν′ – ν″ = 0 bands, (that is ν′ = 0, ν″ = 0; ν′ = 1, ν″ = 1; ν′ = 2, ν″ = 2; …)
start at ≈ 3371 Å.
- This task may be difficult as bands will overlap each other making certain
assignments unclear.

2. Once ν′ and ν″ are assigned to each band, put the wavenumbers into the Deslandres
table.

ν′\ν″ 0 ave. ∆ 1 ave. ∆ 2 ave. ∆ 3 ave. ∆

0 0-0 trn. ←∆→ 1-0 trn. ←∆→ 2-0 trn. ←∆→ 3-0 trn. ←∆→
ave. ∆ ↑∆↓ ↑∆↓ ↑∆↓ ↑∆↓
1 0-1 trn. ←∆→ 1-1 trn. ←∆→ 2-1 trn. ←∆→ 3-1 trn. ←∆→
ave. ∆ ↑∆↓ ↑∆↓ ↑∆↓ ↑∆↓
2 0-2 trn. ←∆→ 1-2 trn. ←∆→ 2-2 trn. ←∆→ 3-2 trn. ←∆→
ave. ∆ ↑∆↓ ↑∆↓ ↑∆↓ ↑∆↓
3 0-3 trn. ←∆→ 1-3 trn. ←∆→ 2-3 trn. ←∆→ 3-3 trn. ←∆→
ave. ∆ ↑∆↓ ↑∆↓ ↑∆↓ ↑∆↓

3. Take the differences between transitions as noted in the table.

Note: Do not put the wavenumbers into the Deslandres table uncritically. If after
placing the wavenumbers into the table, you find that some of the differences
are noticeably different within a particular column or row; then you have
evidence that you have made some bad assignments.

Manipulating Data from Deslandres Table

Each of the average differences (ave. ∆) is a difference between vibrational levels within
the same electronic state. Thus

 2 13 
ave. ∆ = Tν+1 − Tν = ν% e − 2χ eν% e ( ν + 1) + 3y e ν% e  ν + 2ν +  (4)
 12 

4. Prove equation 4 using equation 1 from above. Remember that equation 2 is for two
different electronic states whereas equation 1 is for a single electronic state. Place the
derivation in an appendix.

5. Take the “ave. ∆” from the Deslandres table and use the above equation to make a
redundant system of equations with 3 unknowns, that is ν% e , −2χ eν% e and 3y eν% e .
How many equations you have depends on the quality of your data. Having 5
equations and 3 unknowns would not be unusual.
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6. Using Cramer’s Rule and Mathcad or Maple, solve for 3 equations and 3 unknowns.
- If you have 4 equations and 3 unknowns, solve for the unknowns using all 4
possible combinations of equations and report the average for your unknowns.
- If you have 5 equations and 3 unknowns, solve for the unknowns using all 6
possible combinations of equations and report the average for your unknowns.
This process will yield the spectroscopic constants, ν% e , χe ν% e and ye ν% e , for the upper
and lower electronic states.

7. When the spectroscopic constants are found, ν% 00 can be calculated with the equation 2
from above, by choosing any band from the spectrum.
- Choose several and average results.

8. Compare all the spectroscopic constants to literature values. Cite source of

spectroscopic constants from primary source.

9. Make energy level diagram as on Page 3, label states with quantum numbers, and label
transitions with wavenumber of transition from experimental spectrum. Include as
appendix.

Finding Wavelengths from Spectrum

1. Construct calibration curve

a. Mark far end of film as an origin.
b. Use viewer in instrumental lab to measure distances of spectral lines from origin.
c. Assign Hg lines to known frequencies.
- Use CRC or other source for known emission wavelength of Hg.
d. Create calibration curve with wavelength versus distance data.

2. Use calibration curve and distances to find wavelengths of H lines and N2 band heads.