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Per-Åke Malmqvist

Senior lecturer

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Spin-orbit ab initio study of alkyl halide dissociation via electronic curve crossing

Author

  • D Ajitha
  • M Wierzbowska
  • Roland Lindh
  • Per-Åke Malmqvist

Summary, in English

An ab initio study of the role of electronic curve crossing in the photodissociation dynamics of the alkyl halides is presented. Recent experimental studies show that curve crossing plays a deterministic role in deciding the channel of dissociation. Coupled repulsive potential energy curves of the low-lying n-sigma* states are studied including spin-orbit and relativistic effects. Basis set including effect of core correlation is used. Ab initio vertical excitation spectra of CH3I and CF3I are in agreement with the experimental observation. The curve crossing region is around 2.371 Angstrom for CH3I and CF3I. The potential curves of the repulsive excited states have larger slope for CF3I, suggesting a higher velocity and decreased intersystem crossing probability on fluorination. We also report the potential curves and the region of curve crossing for CH3Br and CH3Cl. (C) 2004 American Institute of Physics.

Department/s

  • Chemical Physics
  • Computational Chemistry

Publishing year

2004

Language

English

Pages

5761-5766

Publication/Series

Journal of Chemical Physics

Volume

121

Issue

12

Document type

Journal article

Publisher

American Institute of Physics (AIP)

Topic

  • Atom and Molecular Physics and Optics
  • Theoretical Chemistry (including Computational Chemistry)

Status

Published

ISBN/ISSN/Other

  • ISSN: 0021-9606