"Vibronic Coupling Of B̃2a′ Electronic State With The X̃2a′, Ã2 A"" Twofold Of Isopropoxy Radical."

Melnik, Dmitry G.

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https://hdl.handle.net/2142/51084 Copy

Description

Title

"Vibronic Coupling Of B̃2a′ Electronic State With The X̃2a′, Ã2 A"" Twofold Of Isopropoxy Radical."

Author(s)

Melnik, Dmitry G.

Contributor(s)

• Liu, Jinjun
• Miller, Terry A.
• Chhantyal-Pun, Rabi
• Roudjane, Mourad

Issue Date

2014-06-17

Keyword(s)

Atmospheric science

Abstract

We performed rotational analyses of previously reported\footnote{R. Chhantyal-Pun and T. A. Miller, \textbf{TD03}, \textit{68$^{th}$ Molecular Spectroscopy Symposium}, Columbus, 2013} vibronic bands belonging to $\tilde{B}^2A' \leftarrow \tilde{X}^2A'$ and $\tilde{B}^2A' \leftarrow \tilde{A}^2A''$ electronic transitions of isopropoxy radical. It is noted that certain vibronic bands belonging to both $\tilde{B}^2A' \leftarrow \tilde{X}^2A'$ and $\tilde{B}^2A' \leftarrow \tilde{A}^2A''$ electronic transitions exhibit unusual rotational contours inconsistent with the electronic symmetry designation of the connecting levels, and the orientation of the electronic transition dipole moment with respect to the principal axis system of the molecule is inconsistent with expectations from the molecule's electronic structure. A coupled, three-electronic-state, vibronic Hamiltonian has been used to account for vibronic interactions between the $\tilde{B}$ electronic state and the $\tilde{X}/ \tilde{A}$ states, whereas an effective rotational Hamiltonian developed earlier\footnote{J. Liu, D. Melnik and T. A. Miller, \textit{J. Chem. Phys.}, \textbf{139}, 094308, (2013)} has been used to describe the rovibronic eigenstates within the $\tilde{X}^2A'$ and $\tilde{A}^2 A''$ twofold. We show that inclusion of the vibronic coupling of the ground twofold to the upper electronic $\tilde{B}$ state is necessary to account for the observed rotational structure anomalies and present molecular parameters resulting from the rotational analysis of the vibronic spectra.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/51084

DOI

https://doi.org/10.15278/isms.2014.TI04

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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