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An H, Choi H, Lee YS, et al. Factors Affecting the Branching Ratio of Photodissociation: Thiophenol Studied through Quantum Wavepacket Dynamics. Chemphyschem. 2015;16(7):1529-34doi: 10.1002/cphc.201500060.
An, H., Choi, H., Lee, Y. S., & Baeck, K. K. (2015). Factors Affecting the Branching Ratio of Photodissociation: Thiophenol Studied through Quantum Wavepacket Dynamics. Chemphyschem : a European journal of chemical physics and physical chemistry, 16(7), 1529-34. https://doi.org/10.1002/cphc.201500060
An, Heesun, et al. "Factors Affecting the Branching Ratio of Photodissociation: Thiophenol Studied through Quantum Wavepacket Dynamics." Chemphyschem : a European journal of chemical physics and physical chemistry vol. 16,7 (2015): 1529-34. doi: https://doi.org/10.1002/cphc.201500060
An H, Choi H, Lee YS, Baeck KK. Factors Affecting the Branching Ratio of Photodissociation: Thiophenol Studied through Quantum Wavepacket Dynamics. Chemphyschem. 2015 May 18;16(7):1529-34. doi: 10.1002/cphc.201500060. Epub 2015 Mar 10. PMID: 25756225.
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Chemphyschem. 2015 May 18;16(7):1529-34. doi: 10.1002/cphc.201500060. Epub 2015 Mar 10.

Factors Affecting the Branching Ratio of Photodissociation: Thiophenol Studied through Quantum Wavepacket Dynamics.

Chemphyschem : a European journal of chemical physics and physical chemistry

Heesun An, Heechol Choi, Yoon Sup Lee, Kyoung Koo Baeck

Affiliations

  1. Department of Chemistry, Gangneung-Wonju National University, Gangwon-Do 210-702 (Republic of Korea).
  2. Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Republic of Korea).
  3. Current address: Plasma Technology Research Center, National Fusion Research Institute (NFRI), Gunsan, Jeollabuk-do 573-540, (Republic of Korea).
  4. Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Republic of Korea). [email protected].
  5. Department of Chemistry, Gangneung-Wonju National University, Gangwon-Do 210-702 (Republic of Korea). [email protected].

PMID: 25756225 DOI: 10.1002/cphc.201500060

Abstract

The photodissociation dynamics of thiophenol (PhSH) excited to the 1(1) ππ* state was investigated by time-dependent quantum wavepacket propagation within two-dimensional (2D) space consisting of the S-H bond and -SH torsion. We systematically studied the dependence of the branching ratio (Ã/X(~)) between the two electronic states of the phenylthiyl radical (PhS(.) ) on several factors of the 2D potential energy surfaces (PESs). The effect of a reduced initial barrier to the first ππ*/πσ* conical intersection (CI) was found to be marginal, whereas the effects of a reduced torsional barrier of -SH on the excited ππ* state and the mitigated slope of the πσ* PES between the first (ππ*/πσ*) and the second (πσ*/S0 ) CIs were noticeable. The effect of the slope on the branching ratio has never been previously noticed. It was shown that the branching ratio can be sufficiently above unity without pre-excitation of the torsion mode of -SH, which has been assumed so far.

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: branching ratio; photochemistry; potential energy surfaces; thiophenol; wavepacket dynamics

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