Theoretical Study Of The Vibrational Spectroscopy Of The Ethyl Radical

Tabor, Daniel P.

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https://hdl.handle.net/2142/50930 Copy

Description

Title

Theoretical Study Of The Vibrational Spectroscopy Of The Ethyl Radical

Author(s)

Tabor, Daniel P.

Contributor(s)

Sibert, Edwin

Issue Date

2014-06-20

Keyword(s)

Theory and Computation

Abstract

The rich spectroscopy of the ethyl radical has attracted the attention of several experimental and theoretical investigations. Its molecular spectrum contains signatures of hyperconjugation, torsion-inversion coupling, and Fermi coupling. We present a full-dimensional theoretical treatment of this vibrational problem using a combination of Van Vleck perturbation theory and variational approaches to further explore these effects. A CCSD(T)/cc-pVTZ potential energy surface and a numerical computation of the kinetic energy operator are employed to construct the Hamiltonian. Our calculations use coordinates that exploit the system's $G_{12}$ PI symmetry to produce compact expressions for the potential energy. This symmetry also allows for a simplified evaluation of the Hamiltonian and greatly reduces the cost of diagonalization. For this talk we illustrate the Van Vleck treatment of the vibrational modes in the ethyl radical and how such a treatment accelerates basis set convergence of the resulting eigenvalues.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/50930

DOI

https://doi.org/10.15278/isms.2014.FC04

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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