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

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [1]
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  1. Univ. of Minnesota, Minneapolis, MN (United States). Department of Chemistry, Chemical Theory Center, and Supercomputing Institute
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States). Department of Chemistry, Chemical Theory Center, and Supercomputing Institute
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1465742
Alternate Identifier(s):
OSTI ID: 1361763
Grant/Contract Number:  
SC0008666; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 6; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Shaohong L., and Truhlar, Donald G. Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole. United States: N. p., 2017. Web. doi:10.1063/1.4975121.
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Li, Shaohong L., & Truhlar, Donald G. Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole. United States. https://doi.org/10.1063/1.4975121
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Li, Shaohong L., and Truhlar, Donald G. Wed . "Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole". United States. https://doi.org/10.1063/1.4975121. https://www.osti.gov/servlets/purl/1465742.
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@article{osti_1465742,
title = {Full-dimensional ground- and excited-state potential energy surfaces and state couplings for photodissociation of thioanisole},
author = {Li, Shaohong L. and Truhlar, Donald G.},
abstractNote = {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.},
doi = {10.1063/1.4975121},
journal = {Journal of Chemical Physics},
number = 6,
volume = 146,
place = {United States},
year = {2017},
month = {2}
}
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https://doi.org/10.1063/1.4975121
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