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J Phys Chem B. 2005 Apr 14;109(14):6491-9.

Optimal choice of dividing surface for the computation of quantum reaction rates.

Author information

  • 1Department of Chemistry and Kenneth S. Pitzer Center for Theoretical Chemistry, University of California, Berkeley, California 94720, USA. cpredescu@comcast.net

Erratum in

  • J Phys Chem B Condens Matter Mater Surf Interfaces Biophys. 2006 Nov 16;110(45):22952.

Abstract

We consider the calculation of quantum mechanical rate constants for chemical reactions via algorithms that utilize short-time values of the symmetrized flux-flux correlation function. We argue that the dividing surface that makes optimal use of the short-time quantum information is the surface that minimizes the value at the origin of the symmetrized flux-flux correlation function. We also demonstrate that, in the classical limit, this quantum variational criterion produces the same dividing surface as Wigner's variational principle. Finally, we argue that the quantum variational criterion behaves in a nearly optimal fashion with respect to the minimization of the extent of re-crossing flux.

PMID:
16851728
[PubMed]
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