Department of Chemistry

The Laser Spectroscopy Facility

70th International Symposium on the Molecular Spectroscopy

June 22-26, 2015

The Laser Spectroscopy FacilityDepartment of Chemistry and Biochemistry

1

2 22

3

Analysis of Rotationally Resolved Spectra to Non-Degenerate ( )

Upper-State Vibronic Levels in the Electronic Transition of NO

a

A E X A

Mourad Rodjane, Terrance Codd, Ming-Wei Chen, Henry Tran, Dmitry Melnik, Terry A. Miller, John F. Stanton

The “important” electronic states of NO3 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′ B2Eb′

B 2Eb′

B 2Ea′

A2Ea′′

X 2A2′

A 2Eb′′

1 2 22

1

4 1 1

15105 cm

e e a

2 1 22

1

4 1 1

7064 cm

e e a

2 2 12

1

4 1 1

0 cm

e e a

W. Eisfeld & K. Morokuma, J. Chem. Phys., 2001, 114, 9430

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′ B2Eb′

B 2Eb′

B 2Ea′

A2Ea′′

X 2A2′

A 2Eb′′

1 2 22

1

4 1 1

15105 cm

e e a

2 1 22

1

4 1 1

7064 cm

e e a

2 2 12

1

4 1 1

0 cm

e e a

pJT pJT

pJT

pJT

Previous Experimental Work on

• Hirota and colleagues reported observation of the 401 and 20

1 bands of the electronically forbidden transitionb

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

• 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 experimentd

• 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 bandse

• 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. A. Weaver, D. W. Arnold, S. E. Bradforth, D. M. Neumark. J. Chem. Phys. 94, 1740 (1991)b. 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)c. A. Deev, J. Sommar, M. Okumura. J. Chem. Phys, 122, 224305 (2005).d. M. E. Jacox, W. E. Thompson. J. Phys. Chem. A, 114, 4712-4718 (2010).e. K. Takematsu, N. C. Eddingsaas, D. J. Robichaud, M. Okumura, Chem. Phys. Lett., 555, 57-63 (2013)f. T. Codd, M.-W. Chen, M. Roudjane, J. F. Stanton, T. A. Miller, J. Chem. Phys., 142, 184305 (2015).

2 22A E X A

2 22A E X A

23A E NO

2 22A E X A

• Observation of the photodetachment spectrum from NO3- to the

states of NO3 by Weaver, et al.a

2 22 and A E X A

• Jet-cooled vibronically resolved NO3 spectraf

'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

𝑎2′

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 discharge(absorption length ℓ = 5 cm)L = 67 cm

Vacuum Pump

ℓ

R ~ 99.995 – 99.999% @ 1.3 m

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

7600 7800 8000 8200 8400 8600wavenumber

a.u.

104

102

204

10

1042

10

10411

03

10

1021

Comparison of Observed and Simulated Line positions1

1 2 3 4

3 3 4 4

718, 682, 1434, 5283.20, 0.25, 0.0, 0.02

cmD K D K

8600 8800 9000 9200 9400 9600wavenumber

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 positions1

1 2 3 4

3 3 4 4

718, 682, 1434, 5283.20, 0.25, 0.0, 0.02

cmD K D K

Characteristics of the Potential Energy Surface from Vibronic Analysis

Study Rotational Structure!

EBar=2295 cm-1BF

EJTSE=5736 cm-1BF

CAL

EJTSE =2999 cm-1CAL

EBar =1093 cm-1CAL

U

v=0

v=1

e

e

a2

a1

No JT JT1+JT2

e

a2

a1

e

Strong JT2

This results in localization inone of three minima, corresponding to a lower symmetry molecular structure.

Degeneracy is ro-vibronic and rotationalstructure corresponds to an asymmetric

top

Near triple degeneracy

Influence of JT Coupling on Rotational Structure

D3h C2v

Matrix Elements in the Vibronic Eigenfunction Basis

1 1

2 2

1 2

1 2

1 2

1 1 1

2 2 2

( ) 00 ( )

( )( )

A E A Ed od od

A E A Ed od od

E A E A E Eod od d odE A E A E Eod od od d

A A E EA H A E H HA H A E H HE H H H E HE H H H H E

The energy difference, ΔEi, is due to Jahn-Teller effects

is rovibronic coupling between different vibronic statesiA EodH

Hd is an oblate symmetric top (B, C) including centrifugal distortion(DJK), spin-orbit (aζed), and spin-rotation (ϵii) terms as necessary denotes the derivative coupling part (Watson term) of the Coriolis interaction in degenerate vibronic states

E EodH

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

ˆev NT V H

evH

7600 7800 8000 8200 8400 8600wavenumber

a.u.

104

102

204

10

1042

10

10411

03

10

1021

Comparison of Observed and Simulated Line positions1

1 2 3 4

3 3 4 4

718, 682, 1434, 5283.20, 0.25, 0.0, 0.02

cmD K D K

Ti:Sa ringcw laser

Ti:Sa Amplifier(2 crystals)

Nd:YAG pulsed laser

Raman Cell

PDInGaAsDetector

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

Vacuum Pump

730 - 930 nm, ~ 1 MHz

50 - 100 mJ ~ 8 - 30 MHz (FT limited)

ℓ

Nd:YVO4

cw laser

R ~ 99.995 – 99.999% @ 1.3 m

SRS (1 m, 13 atm H2, Δν~200 MHz)

20 Hz, 8ns, 350 mJ

HR-JC-CRDS Experimental Setup

BBO

Nd:YAG pulsed laser(seeded)

20 Hz, 8ns, 500 mJ

DFM (Δν~50 MHz)

1-5 mj, <100MHz

Simulation of [1]

[1] Kentarou Kawaguchi, Ryuji. Fujimori, Jian Tang, Takashi Ishiwata. FTIR Spectroscopy of NO3: Perturbation Analysis of the ν3+ν4 State, J. Phys. Chem. A, 117 (50), pp 13732–13742 (2013).

Simulation of [1]

[1] Kentarou Kawaguchi, Ryuji. Fujimori, Jian Tang, Takashi Ishiwata. FTIR Spectroscopy of NO3: Perturbation Analysis of the ν3+ν4 State, J. Phys. Chem. A, 117 (50), pp 13732–13742 (2013).

Simulation of [1]

[1] Kentarou Kawaguchi, Ryuji. Fujimori, Jian Tang, Takashi Ishiwata. FTIR Spectroscopy of NO3: Perturbation Analysis of the ν3+ν4 State, J. Phys. Chem. A, 117 (50), pp 13732–13742 (2013).

Simulation of [1]

[1] Kentarou Kawaguchi, Ryuji. Fujimori, Jian Tang, Takashi Ishiwata. FTIR Spectroscopy of NO3: Perturbation Analysis of the ν3+ν4 State, J. Phys. Chem. A, 117 (50), pp 13732–13742 (2013).

8600 8800 9000 9200 9400 9600wavenumber

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 positions1

1 2 3 4

3 3 4 4

718, 682, 1434, 5283.20, 0.25, 0.0, 0.02

cmD K D K

Simulation of

• Lower rotational temperature. Lines are less dense and spectrum is well simulated.

[1]

[1] Kentarou Kawaguchi, Ryuji. Fujimori, Jian Tang, Takashi Ishiwata. FTIR Spectroscopy of NO3: Perturbation Analysis of the ν3+ν4 State, J. Phys. Chem. A, 117 (50), pp 13732–13742 (2013).

Simulation of [1]

[1] Kentarou Kawaguchi, Ryuji. Fujimori, Jian Tang, Takashi Ishiwata. FTIR Spectroscopy of NO3: Perturbation Analysis of the ν3+ν4 State, J. Phys. Chem. A, 117 (50), pp 13732–13742 (2013).

Simulation of [1]

[1] Kentarou Kawaguchi, Ryuji. Fujimori, Jian Tang, Takashi Ishiwata. FTIR Spectroscopy of NO3: Perturbation Analysis of the ν3+ν4 State, J. Phys. Chem. A, 117 (50), pp 13732–13742 (2013).

Simulation of [1]

[1] Kentarou Kawaguchi, Ryuji. Fujimori, Jian Tang, Takashi Ishiwata. FTIR Spectroscopy of NO3: Perturbation Analysis of the ν3+ν4 State, J. Phys. Chem. A, 117 (50), pp 13732–13742 (2013).

Simulation of • Split lines.

• Probably caused by perturbations from “dark”, high vibrational levels of X state

Comparison of Molecular Parameter for

[2]

[1] E. Hirota, T. Ishiwata, K. Kawaguchi, M. Fujitake, N. Ohashi, and I. Tanaka, J. Chem. Phys, 107, 2829 (1997).[2] Kentarou Kawaguchi, Ryuji. Fujimori, Jian Tang, Takashi Ishiwata. FTIR Spectroscopy of NO3: Perturbation Analysis of the ν3+ν4 State, J. Phys. Chem. A, 117 (50), pp 13732–13742 (2013).

[1]

The value of the effective spin-orbit coupling between X and A states is ~70 cm-1~ ~

All Oblate Symmetric Tops with Zero Spin-orbit Coupling2

3A E NO

Conclusions• Over 20 Vibronic Bands in the Electronic Transition

of NO3 have been Observed and Used to Determine Jahn-Teller Distortion Parameters for a Model Vibronic Hamiltonian

2 22A E X A

Thank You!

• The Structure of Several of These Bands from the Vibrationless Level of the Ground State to Vibronic Levels of the Lowest Excited State has been Rotationally Analyzed with an Oblate Symmetric Top Hamiltonian Yielding Rotational and Spin-rotational Constants. None of these Rotational Analyses Demonstrate Any Jahn-Teller Distortion Nor Any Spin-Orbit Interaction.

• The Rotational Structure (including electronic spin effects) has been Resolved for about Half the Vibronic Bands

• NO3 is a True Multistate, Multimode System with Rich Spectra. However Despite Much Recent Progress There Remain Plenty of Unsolved Problems!

1a

ACKNOWLEDGEMENTS

Post-docs

Graduate Students

Research Scientist

$$$$$$

Ming-Wei Chen – Post-doc UIUC

Rabi Chhantyal Pun – Post-doc U. Bristol, UK

Gabriel Just – Coherent

Jinjun Liu – Faculty, U. Louisville

Dmitry Melnik - LiCor

Neal Kline – US Army Edgewood Chem & Bio Center

Terrance Codd – QC Holding Co.

Mourad Roudjane -OSU

U. S. Department of Energy

Meng Huang- OSU

Henry Tran

Undergraduate Student

John Stanton, Professor, University of Texas at Austin