Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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

Abstract

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.

Authors:
ORCiD logo [1];  [1];  [1]
+ Show Author Affiliations
  1. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry. Chemical Theory Center. Supercomputing Inst.
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1455127
Grant/Contract Number:  
SC0008666
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 17; Journal Issue: 31; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Li, Shaohong L., Xu, Xuefei, and Truhlar, Donald G. Computational simulation and interpretation of the low-lying excited electronic states and electronic spectrum of thioanisole. United States: N. p., 2015. Web. doi:10.1039/c5cp02461g.
Copy to clipboard
Li, Shaohong L., Xu, Xuefei, & Truhlar, Donald G. Computational simulation and interpretation of the low-lying excited electronic states and electronic spectrum of thioanisole. United States. https://doi.org/10.1039/c5cp02461g
Copy to clipboard
Li, Shaohong L., Xu, Xuefei, and Truhlar, Donald G. Fri . "Computational simulation and interpretation of the low-lying excited electronic states and electronic spectrum of thioanisole". United States. https://doi.org/10.1039/c5cp02461g. https://www.osti.gov/servlets/purl/1455127.
Copy to clipboard
@article{osti_1455127,
title = {Computational simulation and interpretation of the low-lying excited electronic states and electronic spectrum of thioanisole},
author = {Li, Shaohong L. and Xu, Xuefei and Truhlar, Donald G.},
abstractNote = {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.},
doi = {10.1039/c5cp02461g},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 31,
volume = 17,
place = {United States},
year = {Fri Jun 05 00:00:00 EDT 2015},
month = {Fri Jun 05 00:00:00 EDT 2015}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/c5cp02461g
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

New coupled-cluster methods with singles, doubles, and noniterative triples for high accuracy calculations of excited electronic states
journal, January 2004

  • Kowalski, Karol; Piecuch, Piotr
  • The Journal of Chemical Physics, Vol. 120, Issue 4
  • DOI: 10.1063/1.1632474

Excited state non-adiabatic dynamics of pyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study
journal, February 2015

  • Wu, Guorong; Neville, Simon P.; Schalk, Oliver
  • The Journal of Chemical Physics, Vol. 142, Issue 7
  • DOI: 10.1063/1.4907529

Excited state deactivation pathways of neutral/protonated anisole and p-fluoroanisole: a theoretical study
journal, January 2014

  • Omidyan, Reza; Rezaei, Hajar
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 23
  • DOI: 10.1039/C4CP00679H

Perspectives on Basis Sets Beautiful: Seasonal Plantings of Diffuse Basis Functions
journal, August 2011

  • Papajak, Ewa; Zheng, Jingjing; Xu, Xuefei
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 10
  • DOI: 10.1021/ct200106a

Diabatic Molecular Orbitals, Potential Energies, and Potential Energy Surface Couplings by the 4-fold Way for Photodissociation of Phenol
journal, July 2013

  • Xu, Xuefei; Yang, Ke R.; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 8
  • DOI: 10.1021/ct400447f

Coupled cluster response functions
journal, September 1990

  • Koch, Henrik; Jo/rgensen, Poul
  • The Journal of Chemical Physics, Vol. 93, Issue 5
  • DOI: 10.1063/1.458814

A quadratically convergent MCSCF method for the simultaneous optimization of several states
journal, May 1981

  • Werner, Hans‐Joachim; Meyer, Wilfried
  • The Journal of Chemical Physics, Vol. 74, Issue 10
  • DOI: 10.1063/1.440892

Quasidegenerate perturbation theory with multiconfigurational self‐consistent‐field reference functions
journal, November 1993

  • Nakano, Haruyuki
  • The Journal of Chemical Physics, Vol. 99, Issue 10
  • DOI: 10.1063/1.465674

Photoinduced Electron and Proton Transfer in Phenol and Its Clusters with Water and Ammonia †
journal, October 2001

  • Sobolewski, Andrzej L.; Domcke, Wolfgang
  • The Journal of Physical Chemistry A, Vol. 105, Issue 40
  • DOI: 10.1021/jp011260l

Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr
journal, May 1989

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

A-band structural dynamics of thioanisole by resonance Raman spectroscopy: A-band structural dynamics of thioanisole
journal, December 2012

  • Liu, Ming-Xia; Xie, Bin-Bin; Li, Ming-Juan
  • Journal of Raman Spectroscopy, Vol. 44, Issue 3
  • DOI: 10.1002/jrs.4213

Experimental and theoretical study of the photodissociation reaction of thiophenol at 243nm: Intramolecular orbital alignment of the phenylthiyl radical
journal, January 2007

  • Lim, Ivan S.; Lim, Jeong Sik; Lee, Yoon Sup
  • The Journal of Chemical Physics, Vol. 126, Issue 3
  • DOI: 10.1063/1.2424939

New exchange-correlation density functionals: The role of the kinetic-energy density
journal, June 2002

  • Boese, A. Daniel; Handy, Nicholas C.
  • The Journal of Chemical Physics, Vol. 116, Issue 22
  • DOI: 10.1063/1.1476309

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980

  • Krishnan, R.; Binkley, J. S.; Seeger, R.
  • The Journal of Chemical Physics, Vol. 72, Issue 1
  • DOI: 10.1063/1.438955

Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon
journal, January 1993

  • Woon, David E.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464303

Vertical transition energies vs. absorption maxima: Illustration with the UV absorption spectrum of ethylene
journal, February 2014

  • Lasorne, Benjamin; Jornet-Somoza, Joaquim; Meyer, Hans-Dieter
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 119
  • DOI: 10.1016/j.saa.2013.04.078

Time-dependent quantum wave-packet description of the π1σ* photochemistry of phenol
journal, June 2005

  • Lan, Zhenggang; Domcke, Wolfgang; Vallet, Valérie
  • The Journal of Chemical Physics, Vol. 122, Issue 22
  • DOI: 10.1063/1.1906218

Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements
journal, October 1982

  • Francl, Michelle M.; Pietro, William J.; Hehre, Warren J.
  • The Journal of Chemical Physics, Vol. 77, Issue 7, p. 3654-3665
  • DOI: 10.1063/1.444267

Excited-state hydrogen detachment and hydrogen transfer driven by repulsive 1πσ* states: A new paradigm for nonradiative decay in aromatic biomolecules
journal, February 2002

  • Sobolewski, A. L.; Domcke, W.; Dedonder-Lardeux, C.
  • Physical Chemistry Chemical Physics, Vol. 4, Issue 7
  • DOI: 10.1039/b110941n

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

High resolution photofragment translational spectroscopy studies of the near ultraviolet photolysis of phenol
journal, October 2006

  • Nix, Michael G. D.; Devine, Adam L.; Cronin, Bríd
  • The Journal of Chemical Physics, Vol. 125, Issue 13
  • DOI: 10.1063/1.2353818

The Construction and Interpretation of Mcscf Wavefunctions
journal, October 1998

Ab initio investigations on the photophysics of indole
journal, December 1999

Experimental probing of conical intersection dynamics in the photodissociation of thioanisole
journal, July 2010

  • Lim, Jeong Sik; Kim, Sang Kyu
  • Nature Chemistry, Vol. 2, Issue 8
  • DOI: 10.1038/nchem.702

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Extended multi-configuration quasi-degenerate perturbation theory: The new approach to multi-state multi-reference perturbation theory
journal, June 2011

  • Granovsky, Alexander A.
  • The Journal of Chemical Physics, Vol. 134, Issue 21
  • DOI: 10.1063/1.3596699

Optimization of parameters for semiempirical methods II. Applications
journal, March 1989

Optimization of parameters for semiempirical methods I. Method
journal, March 1989

Multiwfn: A multifunctional wavefunction analyzer
journal, December 2011

  • Lu, Tian; Chen, Feiwu
  • Journal of Computational Chemistry, Vol. 33, Issue 5
  • DOI: 10.1002/jcc.22885

The influence of polarization functions on molecular orbital hydrogenation energies
journal, January 1973

  • Hariharan, P. C.; Pople, J. A.
  • Theoretica Chimica Acta, Vol. 28, Issue 3
  • DOI: 10.1007/BF00533485

General atomic and molecular electronic structure system
journal, November 1993

  • Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
  • Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
  • DOI: 10.1002/jcc.540141112

Effectiveness of Diffuse Basis Functions for Calculating Relative Energies by Density Functional Theory
journal, March 2003

  • Lynch, Benjamin J.; Zhao, Yan; Truhlar, Donald G.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 9
  • DOI: 10.1021/jp021590l

Intruder state avoidance multireference Møller-Plesset perturbation theory: Multireference Møller-Plesset Perturbation Theory
journal, May 2002

  • Witek, Henryk A.; Choe, Yoong-Kee; Finley, James P.
  • Journal of Computational Chemistry, Vol. 23, Issue 10
  • DOI: 10.1002/jcc.10098

Ab initio characterization of the conical intersections involved in the photochemistry of phenol
journal, December 2008

  • Vieuxmaire, Olivier P. J.; Lan, Zhenggang; Sobolewski, Andrzej L.
  • The Journal of Chemical Physics, Vol. 129, Issue 22
  • DOI: 10.1063/1.3028049

Molecular structure of jet-cooled thioanisole studied by laser-induced fluorescence spectroscopy and ab initio calculations: Planar and/or perpendicular conformation?
journal, May 2008

  • Nagasaka-Hoshino, Mariko; Isozaki, Tasuku; Suzuki, Tadashi
  • Chemical Physics Letters, Vol. 457, Issue 1-3
  • DOI: 10.1016/j.cplett.2008.04.040

Photodissociation Dynamics of Phenol: Multistate Trajectory Simulations including Tunneling
journal, November 2014

  • Xu, Xuefei; Zheng, Jingjing; Yang, Ke R.
  • Journal of the American Chemical Society, Vol. 136, Issue 46
  • DOI: 10.1021/ja509016a

Rotationally resolved high-resolution spectrum of the S1–S0 transition of jet-cooled thioanisole
journal, January 2010

  • Hoshino-Nagasaka, Mariko; Suzuki, Tadashi; Ichimura, Teijiro
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 40
  • DOI: 10.1039/c004454g

Gaussian basis sets for use in correlated molecular calculations. X. The atoms aluminum through argon revisited
journal, June 2001

  • Dunning, Thom H.; Peterson, Kirk A.; Wilson, Angela K.
  • The Journal of Chemical Physics, Vol. 114, Issue 21
  • DOI: 10.1063/1.1367373

Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F
journal, October 1983

  • Clark, Timothy; Chandrasekhar, Jayaraman; Spitznagel, G�nther W.
  • Journal of Computational Chemistry, Vol. 4, Issue 3
  • DOI: 10.1002/jcc.540040303

Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972

  • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
  • DOI: 10.1063/1.1677527
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Photodissociation of phenol in the adiabatic representation: Tunneling, motions of phenyl ring, and kinetic isotope effects
    journal, September 2018

    • He, Ying; Zhao, Huali; Wang, Wenji
    • International Journal of Quantum Chemistry, Vol. 118, Issue 24
    • DOI: 10.1002/qua.25786
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: