A transition-rate investigation by molecular dynamics with the Langevin/implicit-Euler scheme

Abstract

We report results from molecular dynamics simulations for a bistable piecewise-harmonic potential. A new method for molecular dynamics—the Langevin/implicit-Euler scheme—is investigated here and compared to the common Verlet integration algorithm. The implicit scheme introduces new computational and physical features since it (1) does not restrict integration time step to a very small value, and (2) effectively damps vibrational modes ω≫ωc, where ωc is a chosen cutoff frequency. The main issue we explore in this study is how different choices of time steps and cutoff frequencies affect computed transition rates. The one-dimensional, double-well model offers a simple visual and computational opportunity for observing the two different damping forces introduced by the scheme—frictional and intrinsic—and for characterizing the dominating force at a given parameter combination. Another question we examine here is the choice of time step below which the Langevin/implicit-Euler scheme produces ‘‘correct’’ transition rates for a model potential whose energy distribution is ‘‘well-described’’ classically.