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Transient probability currents provide upper and lower bounds on non-equilibrium steady-state currents in the Smoluchowski picture.
Copperman, Jeremy; Aristoff, David; Makarov, Dmitrii E; Simpson, Gideon; Zuckerman, Daniel M.
Afiliação
  • Copperman J; Department of Biomedical Engineering, Oregon Health and Science University, Portland, Oregon 97239, USA.
  • Aristoff D; Department of Mathematics, Colorado State University, Fort Collins, Colorado 80523, USA.
  • Makarov DE; Department of Chemistry and Oden Institute for Computational Engineering and Sciences, University of Texas, Austin, Texas 78712, USA.
  • Simpson G; Department of Mathematics, Drexel University, Philadelphia, Pennsylvania 19104, USA.
  • Zuckerman DM; Department of Biomedical Engineering, Oregon Health and Science University, Portland, Oregon 97239, USA.
J Chem Phys ; 151(17): 174108, 2019 Nov 07.
Article em En | MEDLINE | ID: mdl-31703496
Probability currents are fundamental in characterizing the kinetics of nonequilibrium processes. Notably, the steady-state current Jss for a source-sink system can provide the exact mean-first-passage time (MFPT) for the transition from the source to sink. Because transient nonequilibrium behavior is quantified in some modern path sampling approaches, such as the "weighted ensemble" strategy, there is strong motivation to determine bounds on Jss-and hence on the MFPT-as the system evolves in time. Here, we show that Jss is bounded from above and below by the maximum and minimum, respectively, of the current as a function of the spatial coordinate at any time t for one-dimensional systems undergoing overdamped Langevin (i.e., Smoluchowski) dynamics and for higher-dimensional Smoluchowski systems satisfying certain assumptions when projected onto a single dimension. These bounds become tighter with time, making them of potential practical utility in a scheme for estimating Jss and the long time scale kinetics of complex systems. Conceptually, the bounds result from the fact that extrema of the transient currents relax toward the steady-state current.

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: J Chem Phys Ano de publicação: 2019 Tipo de documento: Article País de afiliação: Estados Unidos

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: J Chem Phys Ano de publicação: 2019 Tipo de documento: Article País de afiliação: Estados Unidos