Optimal choice of dividing surface for the computation of quantum reaction rates.
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.
Predescu
Cristian
C
Department of Chemistry and Kenneth S. Pitzer Center for Theoretical Chemistry, University of California, Berkeley, California 94720, USA. cpredescu@comcast.net
Miller
William H
WH