Escape from a cavity through a small window: turnover of the rate as a function of friction constant.
To escape from a cavity through a small window the particle has to overcome a high entropy barrier to find the exit. As a consequence, its survival probability in the cavity decays as a single exponential and is characterized by the only parameter, the rate constant. We use simulations to study escape of Langevin particles from a cubic cavity through a small round window in the center of one of the cavity walls with the goal of analyzing the friction dependence of the escape rate. We find that the rate constant shows the turnover behavior as a function of the friction constant, zeta: The rate constant grows at very small zeta, reaches a maximum value which is given by the transition-state theory (TST), and then decreases approaching zero as zeta-->infinity. Based on the results found in simulations and some general arguments we suggest a formula for the rate constant that predicts a turnover of the escape rate for ergodic cavities in which collisions of the particle with the cavity walls are defocusing. At intermediate-to-high friction the formula describes transition between two known results for the rate constant: the TST estimation and the high friction limiting behavior that characterizes escape of diffusing particles. In this range of friction the rate constants predicted by the formula are in good agreement with those found in simulations. At very low friction the rate constants found in simulations are noticeably smaller than those predicted by the formula. This happens because the simulations were run in the cubic cavity which is not ergodic.
Berezhkovskii
Alexander M
AM
Mathematical and Statistical Computing Laboratory, Division for Computational Bioscience, Center for Information Technology, National Institutes of Health, Bethesda, Maryland 20892, USA. berezh@mail.nih.gov
Makhnovskii
Yurii A
YA
Zitserman
Vladimir Yu
VY
D055592:Biophysical Phenomena; D001703:Biophysics; D003198:Computer Simulation; D017276:Friction; D007700:Kinetics; D015233:Models, Statistical; D013816:Thermodynamics