Simulating Chemical Kinetics Without Differential Equations: A Quantitative Theory Based on Chemical Pathways

A new approach is presented for simulating the time-evolution of chemically reactive systems. This method provides an alternative to conventional modeling of mass-action kinetics that involves solving differential equations for the species concentrations. The method presented here avoids the need to...

Full description

Saved in:
Bibliographic Details
Published in:The journal of physical chemistry letters 2017-08, Vol.8 (16), p.3826-3833
Main Authors: Bai, Shirong, Skodje, Rex T
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:A new approach is presented for simulating the time-evolution of chemically reactive systems. This method provides an alternative to conventional modeling of mass-action kinetics that involves solving differential equations for the species concentrations. The method presented here avoids the need to solve the rate equations by switching to a representation based on chemical pathways. In the Sum Over Histories Representation (or SOHR) method, any time-dependent kinetic observable, such as concentration, is written as a linear combination of probabilities for chemical pathways leading to a desired outcome. In this work, an iterative method is introduced that allows the time-dependent pathway probabilities to be generated from a knowledge of the elementary rate coefficients, thus avoiding the pitfalls involved in solving the differential equations of kinetics. The method is successfully applied to the model Lotka–Volterra system and to a realistic H2 combustion model.
ISSN:1948-7185
1948-7185
DOI:10.1021/acs.jpclett.7b01760