Document Type

Article

Publication Date

2022

DOI

10.1063/5.0095010

Publication Title

The Journal of Chemical Physics

Volume

156

Issue

21

Pages

214305 (1-13)

Abstract

We report and interpret recently recorded high-resolution infrared spectra for the fundamentals of the CH2 scissors and CH stretches of gas phase cyclopentane at −26.1 and −50 ○C, respectively. We extend previous theoretical studies of this molecule, which is known to undergo barrierless pseudorotation due to ring puckering, by constructing local mode Hamiltonians of the stretching and scissor vibrations for which the frequencies, couplings, and linear dipoles are calculated as functions of the pseudorotation angle using B3LYP/6-311++(d,p) and MP2/cc-pVTZ levels of theory. Symmetrization (D5h) of the vibrational basis sets leads to simple vibration/pseudorotation Hamiltonians whose solutions lead to good agreement with the experiment at medium resolution, but which miss interesting line fractionation when compared to the high-resolution spectra. In contrast to the scissor motion, pseudorotation leads to significant state mixing of the CH stretches, which themselves are Fermi coupled to the scissor overtones.

Rights

© 2022 The Authors. Published under an exclusive license by AIP Publishing.

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in

Sibert, E. L., III., & Bernath, P. F. (2022). A local mode study of ring puckering effects in the infrared spectra of cyclopentane. The Journal of Chemical Physics, 156(21), 1-13, Article 214305.

and may be found at https://doi.org/10.1063/5.0095010

Data Availability

Article states: The data that support the findings of this study are available within the article and its supplementary material.

Original Publication Citation

Sibert, E. L., III., & Bernath, P. F. (2022). A local mode study of ring puckering effects in the infrared spectra of cyclopentane. The Journal of Chemical Physics, 156(21), 1-13, Article 214305. https://doi.org/10.1063/5.0095010

ORCID

0000-0002-1255-396X (Bernath)

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