Analysis of rotationally resolved spectra to degenerate (e′) upper-state vibronic levels in the à 2E′′−X̃2A′2 electronic transition of NO3

Tran, Henry

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https://hdl.handle.net/2142/79138 Copy

Description

Title

Analysis of rotationally resolved spectra to degenerate (e′) upper-state vibronic levels in the à 2E′′−X̃2A′2 electronic transition of NO3

Author(s)

Tran, Henry

Contributor(s)

Miller, Terry A.

Issue Date

23-Jun-15

Keyword(s)

Radicals

Abstract

The vibronic structure of the NO$_3$ radical in the $tilde{A}$ state has been the subject of considerable research in our group and others worldwide. Recently we have collected high resolution, rotationally resolved cavity-ringdown spectra of a number of the vibronic bands terminating on levels of the $widetilde{A}^2E^{primeprime}$ state. Parallel bands to non-degenerate levels of $a_1^{primeprime}$ vibronic symmetry in the $tilde{A}$ state, can mostly be satisfactorily fit using an oblate symmetric top Hamiltonian including the effects of spin rotation. The perpendicular bands, to levels of $e^prime$ symmetry, are not as satisfactorily described using this Hamiltonian. In particular, the rotational structure of the $e^prime$ levels has more transitions than the oblate top model predicts. For this reason we have developed a new rovibronic Hamiltonian capable of analyzing the vibronically degenerate levels. This Hamiltonian is based upon a D$_{3h}$ configuration for NO$_3$ corresponding to rotation of an oblate symmetric top. Terms corresponding to coriolis, spin-rotation, spin-orbit, and Jahn-Teller distortions are then added. The simulations of the $e^prime$ bands using this model show generally better agreement with the high resolution spectra. Our preliminary analysis indicates only modest effects on the rotational structure due to Jahn-Teller distortion. Details of the analysis of the $e^prime$ bands, particularly $2^1_0$, will be presented.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

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http://hdl.handle.net/2142/79138

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