We formulate a general theory of the diffusion-influenced kinetics of irreversible bimolecular reactions occurring in the low concentration limit. Starting from the classical Liouville equation for the reactants and explicit solvent molecules, a formally exact expression for the bimolecular reaction rate coefficient is derived; the structures of reactant molecules and the sink functions may be arbitrarily complicated. The present theoretical formulation shows clearly how the well-known Noyes and Wilemski–Fixman rate theories are related and can be improved in a systematic manner. The general properties of the rate coefficient such as the long-time behavior and the upper and the lower bounds are analyzed. When the reaction can occur at a range of distance, the non-Markovianity of repeated encounter events between a reactant pair becomes significant and either the Noyes theory or the Wilemski–Fixman theory fails. The present theory provides a practical method for calculating the rate expression for such reactions, which improves significantly on the Wilemski–Fixman theory.
Skip Nav Destination
Article navigation
7 July 2009
Research Article|
July 01 2009
A rigorous foundation of the diffusion-influenced bimolecular reaction kinetics
Ji-Hyun Kim;
Ji-Hyun Kim
Department of Chemistry,
Seoul National University
, Seoul 151-747, South Korea
Search for other works by this author on:
Sangyoub Lee
Sangyoub Lee
a)
Department of Chemistry,
Seoul National University
, Seoul 151-747, South Korea
Search for other works by this author on:
a)
Electronic mail: [email protected].
J. Chem. Phys. 131, 014503 (2009)
Article history
Received:
February 18 2009
Accepted:
June 03 2009
Citation
Ji-Hyun Kim, Sangyoub Lee; A rigorous foundation of the diffusion-influenced bimolecular reaction kinetics. J. Chem. Phys. 7 July 2009; 131 (1): 014503. https://doi.org/10.1063/1.3158469
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
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Rubber wear: Experiment and theory
B. N. J. Persson, R. Xu, et al.
Related Content
Kinetics of diffusion-limited catalytically activated reactions: An extension of the Wilemski–Fixman approach
J. Chem. Phys. (November 2005)
Diffusion-influenced reactions involving a reactant with two active sites
J. Chem. Phys. (March 2009)
Generalization of Wilemski-Fixman-Weiss decoupling approximation to the case involving multiple sinks of different sizes, shapes, and reactivities
J. Chem. Phys. (August 2006)
Kinetics of collision-induced reactions between hard-sphere reactants
J. Chem. Phys. (October 2009)
An accurate expression for the rates of diffusion-influenced bimolecular reactions with long-range reactivity
J. Chem. Phys. (April 2013)