Rate coefficient calculation for diffusion-influenced reversible reactions with longer-range reactivities

The chemically relevant so-called phenomenological forward and reverse rate coefficients of reversible bimolecular solution reactions, for nonlocal reactivities defined via attributed irreversible diffusion-kinetic schemes [W. Naumann and A. Molski, J. Chem. Phys. 103, 3474 (1995)], are exactly expr...

Full description

Saved in:
Bibliographic Details
Published in:The Journal of chemical physics 2001-03, Vol.114 (11), p.4791-4795
Main Author: Naumann, Wolfgang
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The chemically relevant so-called phenomenological forward and reverse rate coefficients of reversible bimolecular solution reactions, for nonlocal reactivities defined via attributed irreversible diffusion-kinetic schemes [W. Naumann and A. Molski, J. Chem. Phys. 103, 3474 (1995)], are exactly expressed by formal operator expressions. It is shown that this rate coefficient definition corresponds to the so-called integral encounter theory by Gopich, Kipriyanov, and Doktorov [J. Chem. Phys. 110, 10888 (1999)], an isolated reactive pair approximation. Assuming detailed balance, for the bimolecular isomerization A+B⇌B+C the operator expressions lead to exact relations with the rate coefficients of the irreversible partial reactions A+B→B+C and A+B←B+C. Generalizations of the well-known Noyes formula to reversible reactions result when the corresponding Wilemski-Fixman closure approximations of the irreversible and reversible rate coefficients are inserted.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.1350577