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Title: Rate constants in spatially inhomogeneous systems

Abstract

Here, we introduce a theory and accompanying importance sampling method for computing rate constants in spatially inhomogeneous systems. Using the relationship between rate constants and path space partition functions, we illustrate that the relative change in the rate of a rare event through space is isomorphic to the calculation of a free energy difference, albeit in a trajectory ensemble. Like equilibrium free energies, relative rate constants can be estimated by importance sampling. An extension to transition path sampling is proposed that combines biased path ensembles and weighted histogram analysis to accomplish this estimate. We demonstrate that rate constants can also be decomposed into different contributions, including relative changes in stability, barrier height, and flux. This decomposition provides a means of interpretation and insight into rare processes in complex environments. We confirm these ideas with a simple model of diffusion with spatially varying diffusivity and illustrate their utility in a model of ion pair dissociation near an electrochemical interface.

Authors:
 [1]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21). Scientific Discovery through Advanced Computing (SciDAC)
OSTI Identifier:
1577591
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Schile, Addison J., and Limmer, David T. Rate constants in spatially inhomogeneous systems. United States: N. p., 2019. Web. doi:10.1063/1.5092837.
Schile, Addison J., & Limmer, David T. Rate constants in spatially inhomogeneous systems. United States. doi:10.1063/1.5092837.
Schile, Addison J., and Limmer, David T. Tue . "Rate constants in spatially inhomogeneous systems". United States. doi:10.1063/1.5092837.
@article{osti_1577591,
title = {Rate constants in spatially inhomogeneous systems},
author = {Schile, Addison J. and Limmer, David T.},
abstractNote = {Here, we introduce a theory and accompanying importance sampling method for computing rate constants in spatially inhomogeneous systems. Using the relationship between rate constants and path space partition functions, we illustrate that the relative change in the rate of a rare event through space is isomorphic to the calculation of a free energy difference, albeit in a trajectory ensemble. Like equilibrium free energies, relative rate constants can be estimated by importance sampling. An extension to transition path sampling is proposed that combines biased path ensembles and weighted histogram analysis to accomplish this estimate. We demonstrate that rate constants can also be decomposed into different contributions, including relative changes in stability, barrier height, and flux. This decomposition provides a means of interpretation and insight into rare processes in complex environments. We confirm these ideas with a simple model of diffusion with spatially varying diffusivity and illustrate their utility in a model of ion pair dissociation near an electrochemical interface.},
doi = {10.1063/1.5092837},
journal = {Journal of Chemical Physics},
number = 19,
volume = 150,
place = {United States},
year = {2019},
month = {5}
}

Journal Article:
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