Precision shooting: Sampling long transition pathways

TL;DR

This paper introduces a 'precision shooting' algorithm that improves sampling efficiency of long transition pathways in complex systems by controlling the acceptance ratio of trajectories, demonstrated on a dense liquid isomerization process.

Contribution

The paper presents a novel 'precision shooting' method based on linear short-time disturbances, enhancing transition path sampling for long, rough energy barriers.

Findings

Achieved arbitrary acceptance ratios in trajectory sampling.

Successfully applied to a dense liquid isomerization process.

Discussed applicability to systems with metastable intermediates.

Abstract

The kinetics of collective rearrangements in solution, such as protein folding and nanocrystal phase transitions, often involve free energy barriers that are both long and rough. Applying methods of transition path sampling to harvest simulated trajectories that exemplify such processes is typically made difficult by a very low acceptance rate for newly generated trajectories. We address this problem by introducing a new generation algorithm based on the linear short-time behavior of small disturbances in phase space. Using this ``precision shooting'' technique, arbitrarily small disturbances can be propagated in time, and any desired acceptance ratio of shooting moves can be obtained. We demonstrate the method for a simple but computationally problematic isomerization process in a dense liquid of soft spheres. We also discuss its applicability to barrier crossing events involving metastable intermediate states.