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  4. Quantum dynamics study of the competing ultrafast intersystem crossing and internal conversion in the "channel 3" region of benzene
 
research article

Quantum dynamics study of the competing ultrafast intersystem crossing and internal conversion in the "channel 3" region of benzene

Penfold, T. J.
•
Spesyvtsev, R.
•
Kirkby, O. M.
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2012
Journal Of Chemical Physics

Time-resolved photoelectron spectroscopy can obtain detailed information about the dynamics of a chemical process on the femtosecond timescale. The resulting signal from such detailed experiments is often difficult to analyze and therefore theoretical calculations are important in providing support. In this paper we continue our work on the competing pathways in the photophysics and photochemistry of benzene after excitation into the "channel 3" region [R.S. Minns, D.S.N. Parker, T.J. Penfold, G.A. Worth, and H.H. Fielding, Phys. Chem. Chem. Phys. 12, 15607 (2010)] with details of the calculations shown previously, building on a vibronic coupling Hamiltonian [T.J. Penfold and G.A. Worth, J. Chem. Phys. 131, 064303 (2009)] to include the triplet manifold. New experimental data are also presented suggesting that an oscillatory signal is due to a hot band excitation. The experiments show that signals are obtained from three regions of the potential surfaces, three open channels, which are assigned with the help of simulations showing that following excitation into vibrationally excited-states of S-1 the wavepacket not only crosses through the prefulvenoid conical intersection back to the singlet ground state, but also undergoes ultrafast intersystem crossing to low lying triplet states. The model is, however, not detailed enough to capture the full details of the oscillatory signal due to the hot band. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4767054]

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Type
research article
DOI
10.1063/1.4767054
Web of Science ID

WOS:000312252100035

Author(s)
Penfold, T. J.
Spesyvtsev, R.
Kirkby, O. M.
Minns, R. S.
Parker, D. S. N.
Fielding, H. H.
Worth, G. A.
Date Issued

2012

Publisher

American Institute of Physics

Published in
Journal Of Chemical Physics
Volume

137

Issue

20

Article Number

204310

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LSU  
Available on Infoscience
March 28, 2013
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/91189
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