New shooting algorithms for transition path sampling: centering moves and varied-perturbation sizes for improved sampling.
Transition path sampling has been established as a powerful tool for studying the dynamics of rare events. The trajectory generation moves of this Monte Carlo procedure, shooting moves and shifting modes, were developed primarily for rate constant calculations, although this method has been more extensively used to study the dynamics of reactive processes. We have devised and implemented three alternative trajectory generation moves for use with transition path sampling. The centering-shooting move incorporates a shifting move into a shooting move, which centers the transition period in the middle of the trajectory, eliminating the need for shifting moves and generating an ensemble where the transition event consistently occurs near the middle of the trajectory. We have also developed varied-perturbation size shooting moves, wherein smaller perturbations are made if the shooting point is far from the transition event. The trajectories generated using these moves decorrelate significantly faster than with conventional, constant sized perturbations. This results in an increase in the statistical efficiency by a factor of 2.5-5 when compared to the conventional shooting algorithm. On the other hand, the new algorithm breaks detailed balance and introduces a small bias in the transition time distribution. We have developed a modification of this varied-perturbation size shooting algorithm that preserves detailed balance, albeit at the cost of decreased sampling efficiency. Both varied-perturbation size shooting algorithms are found to have improved sampling efficiency when compared to the original constant perturbation size shooting algorithm.
Rowley
Christopher N
CN
Department of Chemistry, Centre for Catalysis Research and Innovation, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
Woo
Tom K
TK
D000465:Algorithms; D003198:Computer Simulation; D015233:Models, Statistical; D009010:Monte Carlo Method; D012984:Software; D013997:Time Factors