Rovibronic Analysis Of The E′ Bands In The Ã2 E′′ State Of No3 Radical

Tran, Henry

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https://hdl.handle.net/2142/51002 Copy

Description

Title

Rovibronic Analysis Of The E′ Bands In The Ã2 E′′ State Of No3 Radical

Author(s)

Tran, Henry

Contributor(s)

• Miller, Terry A.
• Roudjane, Mourad
• Melnik, Dmitry G.
• Codd, Terrance Joseph

Issue Date

2014-06-16

Keyword(s)

Radicals

Abstract

The vibronic structure of the NO$_3$ radical has been the subject of much recent research in our group.\footnote{Codd, T. et al. 68$^{th}$ Int. Symp. Molec. Spec. (2012)} We have also collected several high resolution spectra of transitions to the $\widetilde{A}^2 E^{\prime\prime}$ state. Parallel bands, with $a_1^{\prime\prime}$ symmetry, have been satisfactorily fit using an oblate symmetric top Hamiltonian with spin rotation. Some lines were seen to be perturbed and it is likely that this is the result of random perturbations from levels originating from the ground electronic state. The perpendicular bands, which have $e^\prime$ symmetry, are not satisfactorily described using this Hamiltonian. In particular the rotational structure of the $e^\prime$ levels has many more transitions than in the oblate top model predicts. For this reason we have developed two different rovibronic Hamiltonians for the analysis of the vibronically degenerate levels. Both include spin-orbit, coriolis, spin-rotation, and Jahn-Teller distortion terms. However, they are derived starting from two different limiting cases. In Case 1 the Hamiltonian is built by assuming first a D$_{3 \textnormal{h}}$ configuration and then perturbations are added. Case 2 starts at the statically distorted, low symmetry geometry and introduces interactions among the vibronic levels. In the case of Jahn-Teller coupling that is neither very weak nor very strong these models should both adequately describe the observed spectra. These models and preliminary analysis of several $e^\prime$ bands are presented.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/51002

DOI

https://doi.org/10.15278/isms.2014.MI12

Copyright and License Information

Copyright 2014 by the authors. Licensed under a Creative Commons Attribution 4.0 International License. http://creativecommons.org/licenses/by/4.0/

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