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Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4975121· OSTI ID:1465742
 [1];  [2]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Department of Chemistry, Chemical Theory Center, and Supercomputing Institute; Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, USA
  2. Univ. of Minnesota, Minneapolis, MN (United States). Department of Chemistry, Chemical Theory Center, and Supercomputing Institute
+ Show Author Affiliations
We present that analytic potential energy surfaces (PESs) and state couplings of the ground and two lowest singlet excited states of thioanisole (C6H5SCH3) are constructed in a diabatic representation based on electronic structure calculations including dynamic correlation. They cover all 42 internal degrees of freedom and a wide range of geometries including the Franck-Condon region and the reaction valley along the breaking S–CH3 bond with the full ranges of the torsion angles. The parameters in the PESs and couplings are fitted to the results of smooth diabatic electronic structure calculations including dynamic electron correlation by the extended multi-configurational quasi-degenerate perturbation theory method for the adiabatic state energies followed by diabatization by the fourfold way. The fit is accomplished by the anchor points reactive potential method with two reactive coordinates and 40 nonreactive degrees of freedom, where the anchor-point force fields are obtained with a locally modified version of the QuickFF package. Finally, the PESs and couplings are suitable for study of the topography of the trilayer potential energy landscape and for electronically nonadiabatic molecular dynamics simulations of the photodissociation of the S–CH3 bond.
Research Organization:
Univ. of Minnesota, Minneapolis, MN (United States). Department of Chemistry, Chemical Theory Center, and Supercomputing Institute
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; SC0008666
OSTI ID:
1465742
Alternate ID(s):
OSTI ID: 1361763
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 146; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Photodissociation of phenol in the adiabatic representation: Tunneling, motions of phenyl ring, and kinetic isotope effects journal September 2018
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Direct diabatization and analytic representation of coupled potential energy surfaces and couplings for the reactive quenching of the excited 2 Σ + state of OH by molecular hydrogen journal September 2019
Full-dimensional three-state potential energy surfaces and state couplings for photodissociation of thiophenol journal October 2019

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