Enhanced Sampling of Configuration and Path Space in a Generalized Ensemble by Shooting Point Exchange
This method addresses the challenge of long time scales in molecular simulations for researchers in computational chemistry, though it appears incremental as it builds on existing transition path sampling techniques.
The authors tackled the problem of simulating rare molecular transitions by proposing a new method that combines transition path sampling with enhanced configuration space exploration, resulting in substantially improved efficiency for systems with multiple transition channels, as demonstrated in the isomerization of proline in a tetrapeptide.
The computer simulation of many molecular processes is complicated by long time scales caused by rare transitions between long-lived states. Here, we propose a new approach to simulate such rare events, which combines transition path sampling with enhanced exploration of configuration space. The method relies on exchange moves between configuration and trajectory space, carried out based on a generalized ensemble. This scheme substantially enhances the efficiency of the transition path sampling simulations, particularly for systems with multiple transition channels, and yields information on thermodynamics, kinetics and reaction coordinates of molecular processes without distorting their dynamics. The method is illustrated using the isomerization of proline in the KPTP tetrapeptide.