Are "bright-state" models appropriate for analyzing fermi-coupled bands in molecular vibrational spectra?

Type of content
Journal Article
Thesis discipline
Degree name
Publisher
American Chemical Society (ACS)
Journal Title
Journal ISSN
Volume Title
Language
eng
Date
2021
Authors
Curnow, Owen
Crittenden, Deborah
Abstract

Bright-state models are often applied to "deperturb"Fermi-coupled bands in molecular vibrational spectra, in cases where a harmonically forbidden transition "borrows"intensity from an energetically nearby allowed transition. However, forbidden transitions can also acquire intensity through anharmonic couplings on the potential energy surface ("mechanical anharmonicity") or dipole moment surface ("electrical anharmonicity") that are not accounted for within the bright-state model. In this work, we compare deperturbation shifts obtained by analysis of experimental data with those predicted using the bright-state model, for a series of discrete encapsulated chloride hydrate isotopomers. Predicted band center shifts and Fermi coupling matrix elements obtained using the bright-state model are larger than those estimated from experimental data.

Description
Citation
Curnow OJ, Crittenden DL (2021). Are "bright-state" models appropriate for analyzing fermi-coupled bands in molecular vibrational spectra?. Journal of Physical Chemistry A. 125(6). 1355-1358.
Keywords
deperturbation analysis, vibrational spectroscopy, chloride hydrates, deuteration, isotopic substitution, Fermi resonance
Ngā upoko tukutuku/Māori subject headings
ANZSRC fields of research
0202 Atomic, Molecular, Nuclear, Particle and Plasma Physics
0306 Physical Chemistry (incl. Structural)
0307 Theoretical and Computational Chemistry
Fields of Research::34 - Chemical sciences::3401 - Analytical chemistry::340101 - Analytical spectrometry
Fields of Research::34 - Chemical sciences::3407 - Theoretical and computational chemistry::340701 - Computational chemistry
Fields of Research::34 - Chemical sciences::3407 - Theoretical and computational chemistry::340704 - Theoretical quantum chemistry
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