2022/07/11 by Florian N. Brünig, Roland R. Netz, Brünig, Florian N. +3 · 1 citation
Physics and Astronomy · #Biological Physics (physics.bio-ph) #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Mesoscale and Nanoscale Physics (cond-mat.mes-hall) #Quantum, superfluid, helium dynamics #Soft Condensed Matter (cond-mat.soft) #Spectroscopy and Quantum Chemical Studies #Statistical Mechanics (cond-mat.stat-mech) #Statistical Mechanics and Entropy
paper · pdf · doi:10.48550/arxiv.2207.04840
openalex publication_date 2022/07/11 · openalex created_date 2023/02/12 · openalex updated_date 2026/07/28
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.