Hamilton-Jacobi equation for the least-action/least-time dynamical path based on fast marching method.
Classical dynamics can be described with Newton's equation of motion or, totally equivalently, using the Hamilton-Jacobi equation. Here, the possibility of using the Hamilton-Jacobi equation to describe chemical reaction dynamics is explored. This requires an efficient computational approach for constructing the physically and chemically relevant solutions to the Hamilton-Jacobi equation; here we solve Hamilton-Jacobi equations on a Cartesian grid using Sethian's fast marching method. Using this method, we can--starting from an arbitrary initial conformation--find reaction paths that minimize the action or the time. The method is demonstrated by computing the mechanism for two different systems: a model system with four different stationary configurations and the H+H(2)-->H(2)+H reaction. Least-time paths (termed brachistochrones in classical mechanics) seem to be a suitable chioce for the reaction coordinate, allowing one to determine the key intermediates and final product of a chemical reaction. For conservative systems the Hamilton-Jacobi equation does not depend on the time, so this approach may be useful for simulating systems where important motions occur on a variety of different time scales.
Department of Chemistry, McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada.
Bijoy K
BK
Dey
Marek R
MR
Janicki
Paul W
PW
Ayers
D000465:Algorithms; D003198:Computer Simulation; D008962:Models, Theoretical