English

Non-Markovianity increases transition path probability

Chemical Physics 2025-01-09 v1 Statistical Mechanics Biological Physics

Abstract

Defining low-dimensional reaction coordinates is crucial for analyzing the dynamics of complex systems and for comparison with experiments. The maximal value of the transition-path probability along the reaction coordinate xx, p(TPx)p(\mathrm{TP}|x), is a common estimator for reaction-coordinate quality by comparing to the theoretical maximal value of 1/2 in the overdamped Markovian limit. We show by analytical arguments and simulations that for non-Markovian dynamics p(TPx)p(\mathrm{TP}|x) is non-monotonic as a function of the memory time and exceeds 1/2 for long memory time. This disqualifies p(TPx)p(\mathrm{TP}|x) as a criterion for reaction coordinate quality.

Keywords

Cite

@article{arxiv.2501.04512,
  title  = {Non-Markovianity increases transition path probability},
  author = {Florian N. Brünig and Benjamin A. Dalton and Jan O. Daldrop and Roland R. Netz},
  journal= {arXiv preprint arXiv:2501.04512},
  year   = {2025}
}
R2 v1 2026-06-28T20:59:52.101Z