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Title: An extended E$$\otimes$$e Jahn-Teller Hamiltonian for large-amplitude motion: Application to vibrational conical intersections in CH 3SH and CH 3OH

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 C 3v symmetry point, an expansion in the spherical harmonics is employed. Application is made to the vibrational Jahn-Teller effect in CH 3XH, 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 C 3v 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 CH 3SH are found in both eclipsed and staggered geometries, whereas those for CH 3OH 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.
Authors:
 [1] ;  [1] ;  [1]
  1. Univ. of Akron, OH (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
FG02-90ER14151
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of Akron, Akron, Ohio (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1473887
Alternate Identifier(s):
OSTI ID: 1372713

Dawadi, Mahesh B., Thapaliya, Bishnu P., and Perry, David S.. An extended E$\otimes$e Jahn-Teller Hamiltonian for large-amplitude motion: Application to vibrational conical intersections in CH3SH and CH3OH. United States: N. p., Web. doi:10.1063/1.4994699.
Dawadi, Mahesh B., Thapaliya, Bishnu P., & Perry, David S.. An extended E$\otimes$e Jahn-Teller Hamiltonian for large-amplitude motion: Application to vibrational conical intersections in CH3SH and CH3OH. United States. doi:10.1063/1.4994699.
Dawadi, Mahesh B., Thapaliya, Bishnu P., and Perry, David S.. 2017. "An extended E$\otimes$e Jahn-Teller Hamiltonian for large-amplitude motion: Application to vibrational conical intersections in CH3SH and CH3OH". United States. doi:10.1063/1.4994699. https://www.osti.gov/servlets/purl/1473887.
@article{osti_1473887,
title = {An extended E$\otimes$e Jahn-Teller Hamiltonian for large-amplitude motion: Application to vibrational conical intersections in CH3SH and CH3OH},
author = {Dawadi, Mahesh B. and Thapaliya, Bishnu P. and Perry, David S.},
abstractNote = {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.},
doi = {10.1063/1.4994699},
journal = {Journal of Chemical Physics},
number = 4,
volume = 147,
place = {United States},
year = {2017},
month = {7}
}