Calculating rotational signatures for Jahn-Teller distorted molecules

Sharma, Ketan

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https://hdl.handle.net/2142/104327 Copy

Description

Title

Calculating rotational signatures for Jahn-Teller distorted molecules

Author(s)

Sharma, Ketan

Contributor(s)

• Stanton, John F.
• Miller, Terry A.
• Garner, Scott M.

Issue Date

2019-06-21

Keyword(s)

Comparing theory and experiment

Abstract

A Jahn-Teller active molecule demonstrates a characteristic signature in its rotationally resolved spectra due to the distortions from the symmetric configuration. In the past decades, this signature has been used to experimentally access and understand the dynamics around a conical intersection. In this talk we present a method to calculate this rotational signature starting with electronic structure calculations. We derive an Effective Rotational Hamiltonian (ERH) for Jahn-Teller active systems and determine the relationship between the experimentally observable rotational parameters and electronic structure theory. The methodology has been further extended to include molecules with significant spin-orbit interaction. We have calculated both $h_1$, which manifests from distortions in the plane perpendicular to the highest symmetry rotational axis of the molecule, and $h_2$, which manifests from out-of-plane distortions of the molecule. We present our findings for cyclopentadienyl (C$_5$H$_5$), methoxy (CH$_3$O) and nitrate (NO$_3$) radicals and compare them to experimental data available in the literature. These calculations not only help guide experiments but are also a great tool for benchmarking high-level quantum chemistry calculations.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Permalink

http://hdl.handle.net/2142/104327

DOI

https://doi.org/10.15278/isms.2019.FF07

Copyright and License Information

Copyright 2019 Ketan Sharma

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