Unbiased computation of transition times by pathway recombination

TL;DR

This paper introduces an unbiased, efficient method for computing transition times in complex systems by recombining trajectory segments, avoiding systematic errors common in existing techniques.

Contribution

A novel trajectory recombination method that accurately computes transition times without systematic errors, applicable to systems with large energy barriers.

Findings

Accurately measured nucleation times over ten orders of magnitude.

Revealed corrections to classical nucleation theory.

Method demonstrated effectively on the Ising model.

Abstract

In many systems, the time scales of the microscopic dynamics and macroscopic dynamics of interest are separated by many orders of magnitude. Examples abound, for instance nucleation, protein folding, and chemical reactions. For these systems, direct simulation of phase space trajectories does not efficiently determine most physical quantities of interest. The last decade has seen the advent of methods circumventing brute force simulation. For most dynamical quantities, these methods all share the drawback of systematical errors. We present a novel method for generating ensembles of phase space trajectories. By sampling small pieces of these trajectories in different phase space domains and piecing them together in a smart way using equilibrium properties, we obtain physical quantities such as transition times. This method does not have any systematic error and is very efficient; the computational effort to calculate the first passage time across a free energy barrier does not increase with the height of the barrier. The strength of the method is shown in the Ising model. Accurate measurements of nucleation times span almost ten orders of magnitude and reveal corrections to classical nucleation theory.