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Title: Full-dimensional three-state potential energy surfaces and state couplings for photodissociation of thiophenol

Abstract

An analytic full-dimensional diabatic potential energy matrix (DPEM) for the lowest three singlet states of thiophenol (C6H5SH) at geometries accessible during photodissociation is constructed using the anchor points reactive potential (APRP) scheme. The data set used for modeling is obtained from electronic structure calculations including dynamic correlation via excitations into the virtual space of a three-state multiconfiguration self-consistent field calculation. The resulting DPEM is a function of all the internal coordinates of thiophenol. The DPEM as a function of the S−H bond stretch and C−C−S−H torsion and the diabatic couplings along two in-plane bend modes and nine out-of-plane distortion modes are computed using extended multiconfigurational quasidegenerate perturbation theory followed by the fourfold way determination of diabatic molecular orbitals and model space diabatization by configurational uniformity, and this dependence of the DPEM is represented by general functional forms. Potentials along 31 tertiary internal degrees of freedom are modeled with system-dependent, primary-coordinate-dependent nonreactive molecular mechanics-type force fields that are parameterized by Cartesian Hessians calculated by generalized Kohn-Sham density functional theory. Adiabatic potential energy surfaces (PESs) and nonadiabatic couplings are obtained by a transformation of the DPEM. The topography of the APRP PESs is characterized by vertical excitation energies, equilibrium geometries, vibrational frequencies,more » and conical intersections, and we find good agreement with available reference data. This analytic DPEM is suitable for full-dimensional electronically nonadiabatic molecular dynamics calculations of the photodissociation of thiophenol with analytic gradients in either the adiabatic or diabatic representation.« less

Authors:
ORCiD logo; ORCiD logo; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1570866
Grant/Contract Number:  
SC0015997
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Name: Journal of Chemical Physics Journal Volume: 151 Journal Issue: 15; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Zhang, Linyao, Truhlar, Donald G., and Sun, Shaozeng. Full-dimensional three-state potential energy surfaces and state couplings for photodissociation of thiophenol. United States: N. p., 2019. Web. doi:10.1063/1.5124870.
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Zhang, Linyao, Truhlar, Donald G., & Sun, Shaozeng. Full-dimensional three-state potential energy surfaces and state couplings for photodissociation of thiophenol. United States. https://doi.org/10.1063/1.5124870
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Zhang, Linyao, Truhlar, Donald G., and Sun, Shaozeng. Fri . "Full-dimensional three-state potential energy surfaces and state couplings for photodissociation of thiophenol". United States. https://doi.org/10.1063/1.5124870.
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@article{osti_1570866,
title = {Full-dimensional three-state potential energy surfaces and state couplings for photodissociation of thiophenol},
author = {Zhang, Linyao and Truhlar, Donald G. and Sun, Shaozeng},
abstractNote = {An analytic full-dimensional diabatic potential energy matrix (DPEM) for the lowest three singlet states of thiophenol (C6H5SH) at geometries accessible during photodissociation is constructed using the anchor points reactive potential (APRP) scheme. The data set used for modeling is obtained from electronic structure calculations including dynamic correlation via excitations into the virtual space of a three-state multiconfiguration self-consistent field calculation. The resulting DPEM is a function of all the internal coordinates of thiophenol. The DPEM as a function of the S−H bond stretch and C−C−S−H torsion and the diabatic couplings along two in-plane bend modes and nine out-of-plane distortion modes are computed using extended multiconfigurational quasidegenerate perturbation theory followed by the fourfold way determination of diabatic molecular orbitals and model space diabatization by configurational uniformity, and this dependence of the DPEM is represented by general functional forms. Potentials along 31 tertiary internal degrees of freedom are modeled with system-dependent, primary-coordinate-dependent nonreactive molecular mechanics-type force fields that are parameterized by Cartesian Hessians calculated by generalized Kohn-Sham density functional theory. Adiabatic potential energy surfaces (PESs) and nonadiabatic couplings are obtained by a transformation of the DPEM. The topography of the APRP PESs is characterized by vertical excitation energies, equilibrium geometries, vibrational frequencies, and conical intersections, and we find good agreement with available reference data. This analytic DPEM is suitable for full-dimensional electronically nonadiabatic molecular dynamics calculations of the photodissociation of thiophenol with analytic gradients in either the adiabatic or diabatic representation.},
doi = {10.1063/1.5124870},
journal = {Journal of Chemical Physics},
number = 15,
volume = 151,
place = {United States},
year = {Fri Oct 18 00:00:00 EDT 2019},
month = {Fri Oct 18 00:00:00 EDT 2019}
}
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https://doi.org/10.1063/1.5124870
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