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Cavity ringdown spectrum of the forbidden (A)over-tilde(2)E('')←(X)over-tilde(2)A(2)(') transition of NO3: Evidence for static Jahn-Teller distortion in the (A)over-tilde state

Deev, Andrei and Sommar, Jonas and Okumura, Mitchio (2005) Cavity ringdown spectrum of the forbidden (A)over-tilde(2)E('')←(X)over-tilde(2)A(2)(') transition of NO3: Evidence for static Jahn-Teller distortion in the (A)over-tilde state. Journal of Chemical Physics, 122 (22). Art. No. 224305. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:DEEjcp05

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Abstract

The Jahn-Teller effect in the first two excited states of the nitrate radical NO3 has yet to be experimentally elucidated. In this paper, direct evidence of strong Jahn-Teller interactions in the A state is presented from the first complete absorption spectrum of the A(2)E(')←X(2)A(2)(') transition of NO3 in the gas phase in the region 5900-9000 cm(-1), at moderate resolution (0.15 cm(-1)). The observed spectrum is consistent with Herzberg-Teller selection rules, and reveals strong linear and quadratic Jahn-Teller interactions in the A state. Several of the vibronic bands have been tentatively assigned, including nu(2),nu(3), an irregular progression in nu(4), and combination bands involving nu(1). Our assignments are consistent with the previous works of Weaver [A. Weaver, D. W. Arnold, S. E. Bradforth, and D. M. Neumark, J. Chem. Phys. 94, 1740 (1991)] and Hirota [E. Hirota, T. Ishiwata, K. Kawaguchi, M. Fujitake, N. Ohashi, and I. Tanaka, J. Phys. Chem. 107, 2829 (1997)] The band origin is not observed, in accord with the selection rules, but is determined to be T-0=7064 cm(-1) from the observation of the 4(1)(0) hot band at 6695.7 cm(-1). Rotational contour analysis of this band indicates that the upper state is an asymmetric rotor, establishing that NO3 undergoes static Jahn-Teller distortion in the ground vibrational level of the A state.


Item Type:Article
Additional Information:©2005 American Institute of Physics. Received 10 January 2005; accepted 3 March 2005; published online 13 June 2005. We acknowledge the support of the NASA UARP Contract No. NAG5-11657, and thank B. J. Drouin for help with software and J. F. Stanton, A. I. Krylov, and T. A. Miller for helpful discussions.
Subject Keywords:Jahn-Teller effect; excited states; ground states; vibronic states; vibrational states; rotational states; free radicals; nitrogen compounds
Record Number:CaltechAUTHORS:DEEjcp05
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:DEEjcp05
Alternative URL:http://dx.doi.org/10.1063/1.1897364
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:4184
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:06 Aug 2006
Last Modified:26 Dec 2012 08:58

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