Simulation of two-dimensional diffusive barrier crossing with a curved reaction path

Richard S. Larson

Physica A: Statistical Mechanics and its Applications, 1986, vol. 137, issue 1, 295-305

Abstract: The crossing of a potential energy barrier by Brownian particles in a system having a curved reaction coordinate is studied by solving numerically the two-dimensional Langevin equation. The activated trajectory method of Northrup and McCammon is used to determine appropriate initial conditions for the simulations and to extract rate constants from the raw data. The calculated crossing rates are in good agreement with those predicted by a formula derived from the two-dimensional Fokker-Planck equation; in particular, they confirm that the reaction path curvature gives rise to an increase in the rate constant for moderate and high degrees of coupling to the heat bath. Examination of individual trajectories shows that this increase results from a tendency for particles to bypass the saddle point of the potential energy surface in favor of a shorter path between the reactant and product states. In the strong-coupling limit, the preferred crossing point agrees well with previous predictions.

Date: 1986
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Persistent link: https://EconPapers.repec.org/RePEc:eee:phsmap:v:137:y:1986:i:1:p:295-305

DOI: 10.1016/0378-4371(86)90077-4

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