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Title: An extended E$$\otimes$$e Jahn-Teller Hamiltonian for large-amplitude motion: Application to vibrational conical intersections in CH3SH and CH3OH

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4994699· OSTI ID:1473887
 [1];  [1];  [1]
  1. Univ. of Akron, OH (United States). Dept. of Chemistry
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An extended E$$\otimes$$e Jahn-Teller Hamiltonian is presented for the case where the (slow) nuclear motion extends far from the symmetry point and may be described approximately as motion on a sphere. Rather than the traditional power series expansion in the displacement from the C3v symmetry point, an expansion in the spherical harmonics is employed. Application is made to the vibrational Jahn-Teller effect in CH3XH, with X = S, O, where the equilibrium CXH angles are 83° and 72°, respectively. In addition to the symmetry-required conical intersection (CI) at the C3v symmetry point, ab initio calculations reveal sets of six symmetry-allowed vibrational CIs in each molecule. The CIs for each molecule are arranged differently in the large-amplitude space, and that difference is reflected in the infrared spectra. The CIs in CH3SH are found in both eclipsed and staggered geometries, whereas those for CH3OH are found only in the eclipsed geometry near the torsional saddle point. Finally, this difference between the two molecules is reflected in the respective high-resolution spectra in the CH stretch fundamental region.

Research Organization:
Univ. of Akron, Akron, Ohio (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-90ER14151
OSTI ID:
1473887
Alternate ID(s):
OSTI ID: 1372713
Journal Information:
Journal of Chemical Physics, Vol. 147, Issue 4; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

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