The stochastic separatrix and the reaction coordinate for complex systems.
We present a new approach to the identification of degrees of freedom which comprise a reaction coordinate in a complex system. The method begins with the generation of an ensemble of reactive trajectories. Each trajectory is analyzed for its equicommittor position or transition state; then the transition state ensemble is identified as the stochastic separatrix. Numerical analysis of the points along the separatrix for variability of coordinate location correctly identifies the components of the reaction coordinate in a test system of a double well coupled to a promoting vibration and a bath of linearly coupled oscillators.
Antoniou
Dimitri
D
Department of Biophysics, Albert Einstein College of Medicine Bronx, New York 10461, USA.
Schwartz
Steven D
SD
D008956:Models, Chemical; D013269:Stochastic Processes; D014732:Vibration