Analysis of Rotationally Resolved Spectra to Non-Degenerate (a1)
Upper-State Vibronic Levels in the A2 E   X 2 A2
Electronic Transition of NO3
70th International Symposium on the
Molecular Spectroscopy
June 22-26, 2015
Mourad Rodjane, Terrance Codd, Ming-Wei Chen, Henry Tran,
Dmitry Melnik, Terry A. Miller, John F. Stanton
The
TheLaser
LaserSpectroscopy
SpectroscopyFacility
Facility
Department
of Chemistry
and Biochemistry
Department
of Chemistry
The “important” electronic states of NO3
THE A-X ELECTRONIC SPECTRUM OF NO3: SOME THEORETICAL RESULTS AND IDEAS
John F. Stanton and Christopher S. Simmons
66th OSU International Symposium on Molecular Spectroscopy, TJ03, June 20-24 ,2011
X̃2A2′
 4e 1e 1a2 
2
2
1
Ã2Ea′′
Ã2Eb′′
B̃2Ea′
X̃2A2′
0 cm1
 4e 1e 1a2 
2
1
2
7064 cm1
Ã2Eb′′
 4e 1e 1a2 
1
Ã2Ea′′
2
15105 cm1
B̃2Ea′
2
B̃2Eb′
W. Eisfeld & K. Morokuma, J. Chem. Phys., 2001, 114, 9430
B̃2Eb′
The “important” electronic states of NO3
THE A-X ELECTRONIC SPECTRUM OF NO3: SOME THEORETICAL RESULTS AND IDEAS
John F. Stanton and Christopher S. Simmons
66th OSU International Symposium on Molecular Spectroscopy, TJ03, June 20-24 ,2011
X̃2A2′
 4e 1e 1a2 
2
2
1
Ã2Ea′′
Ã2Eb′′
X̃2A2′
0 cm1
 4e 1e 1a2 
2
1
2
7064 cm1
 4e 1e 1a2 
1
2
15105 cm1
JT
pJT
3 ,4
3 ,4
pJT
2
pJT
2
JT
B̃2Ea′
2
B̃2Eb′
B̃2Eb′
pJT
JT
Ã2Ea′′
Ã2Eb′′
B̃2Ea′
JT
A true multistate, multimode system with rich spectra and plenty of unsolved problems!
2
A
Previous Experimental Work on E NO3
• Observation of the photodetachment spectrum from NO3- to the A 2 E  and X 2 A2
states of NO3 by Weaver, et al.a
• Hirota and colleagues reported observation of the 401 and 201 bands of the
electronically forbidden A 2 E   X 2 A2 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 A 2 E   X 2 A2 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 A 2 E   X 2 A2 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
• Jet-cooled vibronically resolved NO3 spectraf
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).
NO3 Vibronic Structure and Transitions
Vibronically allowed transitions:

e
  v        e   v   A1
′
e"  v"  𝑎2 (ground state)
 e"   v "    e 
Mode
1
2
3
4
Symmetric
stretch
Umbrella oop
bend
Antisymmetric
stretch
Antisymmetric
ip bend
Symmetry of electric dipole:
or
Symmetry
D3h
a1 '
𝑒′′
𝑎2′′
𝑎1′′
31
42
a2 "
11
e'
𝑒′′
1
2
e'
41
~
0
A 2 E" 0
~
X 2A2'
or
≈≈
≈
≈
𝜇𝑒(∥)
𝜇𝑒(⊥)
𝜇𝑒(∥)
MR-JC-CRDS Experimental Setup
SRS (1 m, 18 atm H2)
20 Hz, 8ns, 500 mJ
Nd:YAG pulse laser
20 Hz, 8ns, 100 mJ
Filters
Sirah Dye Laser
Raman Cell
1st or 2nd Stokes
2-10 mJ,Δν~3 GHz
Ring-down cavity with slit-jet discharge
(absorption length ℓ = 5 cm)
L = 67 cm
PD
InGaAs
Detector
20 m
Fiber Optic
ℓ
R ~ 99.995 – 99.999%
@ 1.3 m
Vacuum Pump
Collimator
Comparison of Observed and Simulated Line positions
1  718, 2  682, 3  1434, 4  528cm 1
D3  3.20, K 3  0.25, D4  0.0, K 4  0.02
4 02
210
210 410
a.u.
4
1
0
110 210
310 110 410
7600
7800
8000
8200
wavenumber
8400
8600
Comparison of Observed and Simulated Line positions
1  718, 2  682, 3  1434, 4  528cm 1
D3  3.20, K 3  0.25, D4  0.0, K 4  0.02
210 430
1
0
a.u.
24
4
8600
3
0
2
0 1 2
0 0
14
210310
2 02 410
310 410
8800
2 30
210310 410
1 2
0 0
23
4 50
2 30 410
310 402
102 410
9000
9200
wavenumber
9400
9600
Characteristics of the Potential Energy
Surface from Vibronic Analysis CAL
CAL
EBar =1093 cm-1
BF
EBar=2295 cm-1
BF
EJTSE=5736 cm-1
CAL
EJTSE =2999
Study Rotational Structure!
cm-1
Influence of JT Coupling on Rotational Structure
No JT
U
JT1+JT2
e
v=1
Strong JT2
a1
e
a1
a2
Near triple
degeneracy
v=0
e
a2
e
D3h
C2v
This results in localization in
one of three minima, corresponding to
a lower symmetry molecular structure.
Degeneracy is ro-vibronic and rotational
structure corresponds to an asymmetric
top
Vibronic Hamiltonian, H ev , for Nuclear Motion on the
Electronic Potential Energy Surface, V
H ev  TˆN  V
Matrix Elements in the Vibronic
Eigenfunction Basis
A1
A2
E
E
A1
H d ( A1 )  E1
0
H odE A1
H odE A1
A2
0
H d ( A2 )  E2
H odE A2
H odE A2
E
E
H odA1E
H odA1E
H odA2 E
H odA2 E
H d ( E ) H odE E
H odE E H d ( E )
The energy difference, ΔEi, is due to Jahn-Teller effects
Hd is an oblate symmetric top (B, C) including centrifugal
distortion(DJK), spin-orbit (aζed), and spin-rotation (ϵii) terms
as necessary
H odE E denotes the derivative coupling part (Watson term) of
the Coriolis interaction in degenerate vibronic states
H odAi E is rovibronic coupling between different vibronic states
Comparison of Observed and Simulated Line positions
1  718, 2  682, 3  1434, 4  528cm 1
D3  3.20, K 3  0.25, D4  0.0, K 4  0.02
4 02
210
210 410
a.u.
4
1
0
110 210
310 110 410
7600
7800
8000
8200
wavenumber
8400
8600
HR-JC-CRDS Experimental Setup
20 Hz, 8ns, 350 mJ
Nd:YAG pulsed laser
50 - 100 mJ
 ~ 8 - 30 MHz (FT limited)
SRS (1 m, 13 atm H2, Δν~200 MHz)
Ti:Sa
Amplifier
(2 crystals)
730 - 930 nm,  ~ 1 MHz
Nd:YVO4
cw laser
Ti:Sa ring
cw laser
Raman Cell
BBO
DFM (Δν~50 MHz)
Ring-down cavity with slit-jet discharge
Nd:YAG pulsed laser
(absorption length ℓ = 5 cm)
(seeded)
L = 67 cm
20 Hz, 8ns, 500 mJ
PD
ℓ
1-5 mj, <100MHz
R ~ 99.995 – 99.999% @ 1.3 m
InGaAs
Detector
Vacuum Pump
Simulation of
[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).
[1]
Simulation of
[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).
[1]
Simulation of
[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).
[1]
Simulation of
[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).
[1]
Comparison of Observed and Simulated Line positions
1  718, 2  682, 3  1434, 4  528cm 1
D3  3.20, K 3  0.25, D4  0.0, K 4  0.02
210 430
1
0
a.u.
24
4
8600
3
0
2
0 1 2
0 0
14
210310
2 02 410
310 410
8800
2 30
210310 410
1 2
0 0
23
4 50
2 30 410
310 402
102 410
9000
9200
wavenumber
9400
9600
[1]
Simulation of
•
Lower rotational temperature. Lines
are less dense and spectrum is well
simulated.
[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).
[1]
Simulation of
[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).
[1]
Simulation of
[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).
[1]
Simulation of
[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 X̃ state
Comparison of Molecular Parameter for A E NO3
2
All Oblate Symmetric Tops with Zero Spin-orbit Coupling
[1]
The value of the effective spin-orbit coupling between ~X and A~ states is ~70 cm-1
[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).
[2]
Conclusions
• Over 20 Vibronic Bands in the A 2 E   X 2 A2 Electronic Transition
of NO3 have been Observed and Used to Determine Jahn-Teller
Distortion Parameters for a Model Vibronic Hamiltonian
• The Rotational Structure (including electronic spin effects) has
been Resolved for about Half the Vibronic Bands
• The Structure of Several of These Bands from the Vibrationless
Level of the Ground State to a1 Vibronic Levels of the Lowest
Excited State has been Rotationally Analyzed with an Oblate
Symmetric Top Hamiltonian Yielding Rotational and Spinrotational Constants. None of these Rotational Analyses
Demonstrate Any Jahn-Teller Distortion Nor Any Spin-Orbit
Interaction.
• NO3 is a True Multistate, Multimode System with Rich Spectra.
However Despite Much Recent Progress There Remain Plenty
of Unsolved Problems!
Thank You!
ACKNOWLEDGEMENTS
Graduate Students
Undergraduate Student
Terrance Codd – QC Holding Co.
Henry Tran
Post-docs
Neal Kline – US Army
Edgewood Chem & Bio Center
Mourad Roudjane -OSU
Meng Huang- OSU
Jinjun Liu –
John Stanton, Professor,
Faculty, U. Louisville
Ming-Wei Chen –
Post-doc UIUC
University of Texas at Austin
Rabi Chhantyal Pun –
Post-doc U. Bristol, UK
Research Scientist
Gabriel Just –
Coherent
Dmitry Melnik - LiCor
$$$$$$
U. S. Department of Energy