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Journal of Chemical Physics / Volume 135 / Issue 23 / ARTICLES / Theoretical Methods and Algorithms

J. Chem. Phys. 135, 234106 (2011); http://dx.doi.org/10.1063/1.3667203 (14 pages)

Nonequilibrium Fermi golden rule for electronic transitions through conical intersections

Artur F. Izmaylov1, David Mendive–Tapia2, Michael J. Bearpark2, Michael A. Robb2, John C. Tully1, and Michael J. Frisch3

1Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA
2Department of Chemistry, Imperial College London, London SW7 2AZ, United Kingdom
3Gaussian, Inc., Wallingford, Connecticut 06492, USA

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(Received 20 September 2011; accepted 18 November 2011; published online 19 December 2011)

We consider photoinduced electronic transitions through conical intersections in large molecules. Starting from the linear vibronic model Hamiltonian and treating linear diabatic couplings within the second order cumulant expansion, we have developed a simple analytical expression for the time evolution of electronic populations at finite temperature. The derived expression can be seen as a nonequilibrium generalization of the Fermi golden rule due to a nonequilibrium character of the initial photoinduced nuclear distribution. All parameters in our model are obtained from electronic structure calculations followed by a diabatization procedure. The results of our model are found to agree well with those of quantum dynamics for a test set of systems: fulvene molecule, 2,6-bis(methylene) adamantyl cation, and its dimethyl derivative.

© 2011 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. PROCEDURE
  3. NUMERICAL SIMULATIONS
    1. Fulvene
      1. Nonequilibrium dynamics
      2. Temperature dependence
    2. 2,6-bis(methylene) adamantyl radical cation and its dimethyl derivative
      1. Equilibrium dynamics
      2. Nonequilibrium dynamics
      3. Temperature dependence
  4. CONCLUSION

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KEYWORDS and PACS

Keywords

organic compounds, vibronic states

PACS

  • 33.20.Wr

    Vibronic, rovibronic, and rotation-electron-spin interactions

  • 31.15.bt

    Statistical model calculations (including Thomas-Fermi and Thomas-Fermi-Dirac models)

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3667203

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
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