Rotational parameters from vibronic eigenfunctions of Jahn-Teller active molecules

Garner, Scott M.

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https://hdl.handle.net/2142/96822 Copy

Description

Title

Rotational parameters from vibronic eigenfunctions of Jahn-Teller active molecules

Author(s)

Garner, Scott M.

Contributor(s)

Miller, Terry A.

Issue Date

2017-06-19

Keyword(s)

Multiple potential energy surfaces

Abstract

The structure in rotational spectra of many free radical molecules is complicated by Jahn-Teller distortions. Understanding the magnitudes of these distortions is vital to determining the equilibrium geometric structure and details of potential energy surfaces predicted from electronic structure calculations. For example, in the recently studied {footnotesize $widetilde{A}^2E^{primeprime}$ } state of the NO$_3$ radical, the magnitudes of distortions are yet to be well understood as results from experimental spectroscopic studies of its vibrational and rotational structure disagree with results from electronic structure calculations of the potential energy surface. By fitting either vibrationally resolved spectra or vibronic levels determined by a calculated potential energy surface, we obtain vibronic eigenfunctions for the system as linear combinations of basis functions from products of harmonic oscillators and the degenerate components of the electronic state. Using these vibronic eigenfunctions we are able to predict parameters in the rotational Hamiltonian such as the Watson Jahn-Teller distortion term, $h_1$, and compare with the results from the analysis of rotational experiments.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Permalink

http://hdl.handle.net/2142/96822

DOI

https://doi.org/10.15278/isms.2017.MG05

Copyright and License Information

Copyright 2017 Scott M. Garner

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