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Computational simulation and interpretation of the low-lying excited electronic states and electronic spectrum of thioanisole

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/c5cp02461g· OSTI ID:1455127
 [1];  [2];  [2]
  1. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry. Chemical Theory Center. Supercomputing Inst.; Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry. Chemical Theory Center. Supercomputing Inst.
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Three singlet states, namely a closed-shell ground state and two excited states with 1ππ* and 1nσ* character, have been suggested to be responsible for the radiationless decay or photochemical reaction of photoexcited thioanisole. The correct interpretation of the electronic spectrum is critical for understanding the character of these low-lying excited states, but the experimental spectrum is yet to be fully interpreted. In the work reported here, we investigated the nature of those three states and a fourth singlet state of thioanisole using electronic structure calculations by multireference perturbation theory, by completely-renormalized equation-of-motion coupled cluster theory with single and double excitations and noniterative inclusion of connected triples (CR-EOM-CCSD(T)), and by linear-response time-dependent density functional theory (TDDFT). We clarified the assignment of the electronic spectrum by simulating it using a normal-mode sampling approach combined with TDDFT in the Tamm–Dancoff approximation (TDA). The understanding of the electronic states and of the accuracy of the electronic structure methods lays the foundation of our future work of constructing potential energy surfaces.

Research Organization:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0008666
OSTI ID:
1455127
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 31 Vol. 17; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

Correction: MN15: A Kohn–Sham global-hybrid exchange–correlation density functional with broad accuracy for multi-reference and single-reference systems and noncovalent interactions journal January 2016
Photodissociation of phenol in the adiabatic representation: Tunneling, motions of phenyl ring, and kinetic isotope effects journal September 2018
MN15: A Kohn–Sham global-hybrid exchange–correlation density functional with broad accuracy for multi-reference and single-reference systems and noncovalent interactions journal January 2016

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