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Title: 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

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 Office of Science (SC), Basic Energy Sciences (BES); USDOE
Grant/Contract Number:
SC0008666; AC02-05CH11231
OSTI ID:
1465742
Alternate ID(s):
OSTI ID: 1361763
Journal Information:
Journal of Chemical Physics, Vol. 146, Issue 6; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 26 works
Citation information provided by
Web of Science

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Full-dimensional three-state potential energy surfaces and state couplings for photodissociation of thiophenol journal October 2019