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Title: Ab initio characterization of the conical intersections involved in the photochemistry of phenol

Abstract

The nature of the vibronic interactions between the {sup 1}{pi}{pi}* (A{sup '}), the {sup 1}{pi}{sigma}* (A{sup ''}), and the S{sub 0} (A{sup '}) states at the CI{sub {pi}}{sub {pi}}{sub */{pi}}{sub {sigma}}{sub *} and CI{sub {pi}}{sub {sigma}}{sub */{pi}}{sub {pi}} conical intersections has been investigated by accurate ab initio calculations. Potential energy surfaces have been constructed at the complete-active-space self-consistent-field and multireference configuration-interaction (MRCI) levels of theory along each of the ten normal coordinates of A{sup ''} symmetry that potentially can be coupling modes at these conical intersections. The OH torsion was found to be by far the strongest coupling mode in each case. As for benzene, a 'channel three' radiationless decay mechanism associated with a prefulvenic conical intersection, CI{sub pref}, was found to exist in phenol. The reaction path connecting the prefulvenic form of phenol with the minimum-energy structure of the S{sub 1} state was computed at different levels of theory. The barrier to be overcome for the opening of the prefulvenic decay channel is estimated as 6370 cm{sup -1} at the MRCI level, that is, about 2300 cm{sup -1} above the energy of CI{sub {pi}}{sub {pi}}{sub */{pi}}{sub {sigma}}{sub *}. With sufficient excess energy in the S{sub 1} state, the prefulvenicmore » decay mechanism can be in competition with the hydrogen detachment process.« less

Authors:
;  [1];  [2];  [3]
  1. Department of Chemistry, Technische Universitaet Muenchen, D-85747 Garching (Germany)
  2. Max-Planck-Institut fuer Kohlenforschung, D-45470 Muelheim an der Ruhr (Germany)
  3. Institute of Physics, Polish Academy of Sciences, PL-02668 Warsaw (Poland)
Publication Date:
OSTI Identifier:
21254942
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 129; Journal Issue: 22; Other Information: DOI: 10.1063/1.3028049; (c) 2008 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; BENZENE; CONFIGURATION INTERACTION; COORDINATES; COUPLING; INTERACTIONS; PHENOL; PHOTOCHEMISTRY; RADIATIONLESS DECAY; SELF-CONSISTENT FIELD; STRONG-COUPLING MODEL; SURFACES

Citation Formats

Vieuxmaire, Olivier P. J., Domcke, Wolfgang, Lan, Zhenggang, and Sobolewski, Andrzej L. Ab initio characterization of the conical intersections involved in the photochemistry of phenol. United States: N. p., 2008. Web. doi:10.1063/1.3028049.
Vieuxmaire, Olivier P. J., Domcke, Wolfgang, Lan, Zhenggang, & Sobolewski, Andrzej L. Ab initio characterization of the conical intersections involved in the photochemistry of phenol. United States. https://doi.org/10.1063/1.3028049
Vieuxmaire, Olivier P. J., Domcke, Wolfgang, Lan, Zhenggang, and Sobolewski, Andrzej L. 2008. "Ab initio characterization of the conical intersections involved in the photochemistry of phenol". United States. https://doi.org/10.1063/1.3028049.
@article{osti_21254942,
title = {Ab initio characterization of the conical intersections involved in the photochemistry of phenol},
author = {Vieuxmaire, Olivier P. J. and Domcke, Wolfgang and Lan, Zhenggang and Sobolewski, Andrzej L},
abstractNote = {The nature of the vibronic interactions between the {sup 1}{pi}{pi}* (A{sup '}), the {sup 1}{pi}{sigma}* (A{sup ''}), and the S{sub 0} (A{sup '}) states at the CI{sub {pi}}{sub {pi}}{sub */{pi}}{sub {sigma}}{sub *} and CI{sub {pi}}{sub {sigma}}{sub */{pi}}{sub {pi}} conical intersections has been investigated by accurate ab initio calculations. Potential energy surfaces have been constructed at the complete-active-space self-consistent-field and multireference configuration-interaction (MRCI) levels of theory along each of the ten normal coordinates of A{sup ''} symmetry that potentially can be coupling modes at these conical intersections. The OH torsion was found to be by far the strongest coupling mode in each case. As for benzene, a 'channel three' radiationless decay mechanism associated with a prefulvenic conical intersection, CI{sub pref}, was found to exist in phenol. The reaction path connecting the prefulvenic form of phenol with the minimum-energy structure of the S{sub 1} state was computed at different levels of theory. The barrier to be overcome for the opening of the prefulvenic decay channel is estimated as 6370 cm{sup -1} at the MRCI level, that is, about 2300 cm{sup -1} above the energy of CI{sub {pi}}{sub {pi}}{sub */{pi}}{sub {sigma}}{sub *}. With sufficient excess energy in the S{sub 1} state, the prefulvenic decay mechanism can be in competition with the hydrogen detachment process.},
doi = {10.1063/1.3028049},
url = {https://www.osti.gov/biblio/21254942}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 22,
volume = 129,
place = {United States},
year = {Sun Dec 14 00:00:00 EST 2008},
month = {Sun Dec 14 00:00:00 EST 2008}
}