Terrance J. Codd*, John Stanton†, and Terry A.

Miller*

Vibronic Analysis of the State of NO3

* The Laser Spectroscopy Facility, Department of Chemistry and Biochemistry The Ohio State University, Columbus, Ohio

† Department of Chemistry, The University of Texas at Austin, Austin, Texas

Previous Work Hirota and colleagues reported observation of the 40

1 and 201 bands of the

electronically forbidden transitiona

First broad range spectrum was taken by Deev et al. in an ambient CRDS experimentb

Several bands were assigned in this work and evidence of strong JT coupling was reported

Jacox and Thompson recorded FTIR spectra of the transition in a Ne matrix experimentc

It significantly extended the spectral range and made several more assignments

They reported evidence of weak JT coupling in 4

Most recently, Takematsu et al. have reported the observation of the vibronically forbidden origin of the transition and observed several hot bandsd

They refined the position of the origin band to 7062.25 cm-1 and reported a second peak roughly 8 cm-1 to the blue

a. K. Kawaguchi, T. Ishiwata, E. Hirota, I. Tanaka. Chem. Phys. 231, 193 (1998). E. Hirota, T. Ishiwata, K. Kawaguchi, M. Fujitake, N. Ohashi, I. Tanaka. J. Chem. Phys. 107, 2829 (1997)b. A. Deev, J. Sommar, M. Okumura. J. Chem. Phys, 122, 224305 (2005).c. M. E. Jacox, W. E. Thompson. J. Phys. Chem. A, 114, 4712-4718 (2010).d. K. Takematsu, N. C. Eddingsaas, D. J. Robichaud, M. Okumura, Chem. Phys. Lett., 555, 57-63 (2013)

2 22A E X A

2 22A E X A

23A E NO

2 22A E X A

The “important” electronic states of NO3THE A-X ELECTRONIC SPECTRUM OF NO3: SOME THEORETICAL RESULTS AND IDEASJohn F. Stanton and Christopher S. Simmons66th OSU International Symposium on Molecular Spectroscopy, TJ03, June 20-24 ,2011

X ̃2A2′ A ̃2Ea′′ A ̃2Eb′′ B ̃2Ea′ B ̃2Eb′

B ̃2Eb′

B ̃2Ea′

A ̃2Ea′′

X ̃2A2′

A ̃2Eb′′

1 2 2

2

1

4 1 1

15105 cm

e e a

2 1 2

2

1

4 1 1

7064 cm

e e a

2 2 1

2

1

4 1 1

0 cm

e e a

The “important” electronic states of NO3

2

2

3 ,4 3 ,4

JT

JT

JT

JT

A true multistate, multimode system with rich spectra and plenty of unsolved problems!

THE A-X ELECTRONIC SPECTRUM OF NO3: SOME THEORETICAL RESULTS AND IDEASJohn F. Stanton and Christopher S. Simmons66th OSU International Symposium on Molecular Spectroscopy, TJ03, June 20-24 ,2011

X ̃2A2′ A ̃2Ea′′ A ̃2Eb′′ B ̃2Ea′ B ̃2Eb′

B ̃2Eb′

B ̃2Ea′

A ̃2Ea′′

X ̃2A2′

A ̃2Eb′′

1 2 2

2

1

4 1 1

15105 cm

e e a

2 1 2

2

1

4 1 1

7064 cm

e e a

2 2 1

2

1

4 1 1

0 cm

e e a

'2

2~AX

00

14

24

12

≈≈ ≈"

~2EA

(ground state)

eve ""

"" ve

    

 

𝑒 ′ ′11

𝑒 ′ ′𝑎 2′ ′𝑎1 ′ ′

13

≈

Mode Symmetry D3h

1 Symmetric stretch

'1a

2 Umbrella oop bend

"2a

3 Antisymmetric stretch

'e

4 Antisymmetric ip bend

'e

NO3 Vibronic Structure and Transitions

or Symmetry of electric dipole: or

Vibronically allowed transitions: 1e v e v A

Nd:YAG pulse laser Raman Cell

PDInGaAsDetector

Ring-down cavity with slit-jet(absorption length ℓ = 5 cm)L = 67 cm

Vacuum Pump

ℓ

R ~ 99.995 – 99.999% @ 1.3 mm

SRS (1 m, 18 atm H2)20 Hz, 8ns, 500 mJ

MR-JC-CRDS Experimental Setup

Sirah Dye LaserFilters

1st or 2nd Stokes2-10 mJ,Δν~3 GHz

Collimator

20 Hz, 8ns, 100 mJ

20 m Fiber Optic

7500 7600 7700 7800 7900 8000 8100 8200 8300 8400

wavenumber

7500 7600 7700 7800 7900 8000 8100 8200 8300 8400

wavenumber7500 7600 7700 7800 8100 8200 8300 8400

wavenumber

Room Temperature

Jet Cooled

Room Temperature vs Jet-Cooled Spectra

Room temperature data from:A. Deev, J. Sommar, M. Okumura. J. Chem. Phys, 122, 224305 (2005).

7600 7800 8000 8200 8400 8600

a.u

.

wavenumber (cm-1)

wavenumber (cm-1)

a.u

.

8800 9000 9200 9400 9600

Jet-Cooled CRDS Data

Vibronic Hamiltonian, , for Nuclear Motion on theElectronic Potential Energy Surface, V

ˆev NT V H

evH

3D Plot of V showing Jahn-Teller Distortion

Quadratic Vibronic Hamiltonian3 6 2

2 2,

1 1 ,

1 1ˆ | | | |2 2

N p p

N i i i i ri i r

T Q Q

T. A. Barckholtz, T. A. Miller, Int Rev in Phys. Chem.17, 435-524 (1998)

,1 ,

p

i i ri r

k Q

2,

1 ,

1( )

2

p

ii i ri r

g Q

,1 1 ,

1

2

ps

ij i r jj i r

b Q Q

,

, ,1 1 ,

1( )

2

p p j i

ij i r j ri j r

c Q Q

Harmonic Oscillator

Linear Jahn-Teller

Quadratic Jahn-Teller

Cross-Quadratic Jahn-Teller

Bi-linear Coupling

ev H

Vibronic Parameters

2

, , 0

ii i

V

Q Q

2

, , 0

iii j

Vg

Q Q

, 0

ii

Vk

Q

2

, 0

iji j

Vb

Q Q

2

32i i

ii

k MD

iii

i

gK

Hamiltonian Parameters

Experimental Parameters

2

, , 0

iji j

Vc

Q Q

0,0,1,0|

0,1,0,1|1,0,0,1|

State Vibronic Interactions

1,1,0,0|

0,1,0,0|

0,0,0,0|

1,0,0,0|D3

D3

D4

D4

c3,4

c3,4

c3,4

b1,3

b1,3

b1,4

b1,4

443321 ,,,,,|| ll

K4

K3,K4

K3,K4

K3,K4

K3

7600 7800 8000 8200 8400 8600

a.u

.

wavenumber (cm-1)

wavenumber (cm-1)

a.u

.

8800 9000 9200 9400 9600

104

102

204

10

1042

10

10411

03

10

1021

304 1 1

0 03 4

20

1042

20

1041

10

2042

1 10 02 3

302

10

2041

1 20 03 4

1 30 02 4

1 1 10 0 02 3 4

10

3042

504

1 20 02 3

Vibronic Assignments

'2

2~AX

14

12

e

1 12 4

≈

e

≈≈

Complementary of Parallel and Perpendicular Bands

= 21 vibrationalfrequency

This means that we can use the observed perpendicular combination bands to find the position of the components of the degenerate modes.

(vibrational symmetry )

(41 vibronic levels x )

e

e1a

2a

2a

2a

1ae

2a

"~2EA e

7600 7800 8000 8200 8400 8600

wavenumber

a.u

.

104

102

204

10

1042

10

10411

03

10

1021

Comparison of Observed and Simulated Line positions

8600 8800 9000 9200 9400 9600

wavenumber

a.u

.

304

1 10 03 4

20

1042 2

01041

10

2042

1 10 02 3

302

10

2041

1 20 03 4

1 30 02 4

1 1 10 0 02 3 4

10

3042

5041 2

0 02 3

Comparison of Observed and Simulated Line positions

Comparison of Observed and Calculated (John Stanton) Line Positions (Parallel Bands Only)

Further work clearly needed

Conclusions

• Over 20 Vibronic Bands in the Electronic Transition have been Observed and Assigned

2 22A E X A

• The Structure of the State has been Well Stimulated Including Linear and Quadratic Vibronic Interaction Terms

2A E

• Harmonic Frequencies for All 4 Vibrational Modes and Jahn-Teller Parameters for the e' Modes have been Obtained

• More Detailed Comparison to Calculations Forthcoming Imminently