Properties of chemical reactions in systems undergoing diffusional motion depend on the ratio of chemical to diffusional rates. The present work deals with perturbation expansions in this quantity. For bounded diffusion, the Laplace transformed survival probability, mean lifetime, eigenvalues, and eigenfunctions are expanded in this ratio. The theory is developed mainly in the fast diffusion limit. In this limit, the survival probability for an initial equilibrium state is shown to be exponential up to linear order. For unbounded diffusion, expansions are derived for the steady‐state concentration profile and rate coefficient. By inverting the series one obtains Padé‐like approximations for rate coefficients with much improved convergence. Several examples are worked out in detail. These include the ‘‘radiation’’ boundary condition, barrierless isomerization, steady‐state binding, and Förster quenching.
Skip Nav Destination
Article navigation
1 April 1989
Research Article|
April 01 1989
Viscosity expansions in reactive diffusion processes Available to Purchase
Noam Agmon
Noam Agmon
Physical Sciences Laboratory, DCRT, and Laboratory of Chemical Physics, NIDDK, National Institutes of Health, Bethesda, Maryland 20892
Search for other works by this author on:
Noam Agmon
Physical Sciences Laboratory, DCRT, and Laboratory of Chemical Physics, NIDDK, National Institutes of Health, Bethesda, Maryland 20892
J. Chem. Phys. 90, 3765–3775 (1989)
Article history
Received:
August 12 1988
Accepted:
December 16 1988
Citation
Noam Agmon; Viscosity expansions in reactive diffusion processes. J. Chem. Phys. 1 April 1989; 90 (7): 3765–3775. https://doi.org/10.1063/1.456650
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.