Barrier-crossing times for different non-Markovian friction in well and barrier $-$ A numerical study

TL;DR

This study introduces a generalized Langevin model to analyze how different non-Markovian effects in the well and barrier regions influence barrier-crossing times, revealing regimes where memory effects either accelerate or decelerate the process.

Contribution

The paper develops a numerical model that interpolates between existing theories and tests an analytic rate theory, providing new insights into non-Markovian effects on barrier crossing.

Findings

Short barrier memory decreases crossing time compared to long barrier memory.

Long well-memory can slow down barrier crossing, contrary to some theories.

Both Markovian and non-Markovian effects influence crossing times, explained by a committor analysis.

Abstract

We introduce a generalized Langevin model system for different non-Markovian effects in the well and barrier regions of a potential, and use it to numerically study the dependence of the barrier-crossing time. In the appropriate limits, our model interpolates between the theoretical barrier-crossing-time predictions by Grote and Hynes (GH), as well as by Pollak et al., which for a single barrier memory time can differ by several orders of magnitude. Our model furthermore allows to test an analytic rate theory for space-inhomogeneous memory, which disagrees with our numerical results in the long well-memory regime. In this regime, we find that short barrier memory decreases the barrier-crossing time as compared to long barrier memory. This is in contrast with the short well-memory regime, where both our numerical results and GH theory predict an acceleration of the barrier crossing time with increasing barrier memory time. Both effects, the `Markovian-barrier acceleration' and GH `non-Markovian-barrier acceleration' can be understood from a committor analysis. Our model combines finite relaxation times of orthogonal degrees of freedom with a space-inhomogeneous coupling to such degrees, and represents a step towards more realistic modeling of physical reaction coordinates.