Metabasin approach for computing the master equation dynamics of systems with broken ergodicity

John C. Mauro, Roger J. Loucks, Prabhat K. Gupta

55 Scopus citations

Abstract

We propose a technique for computing the master equation dynamics of systems with broken ergodicity. The technique involves a partitioning of the system into components, or metabasins, where the relaxation times within a metabasin are short compared to an observation time scale. In this manner, equilibrium statistical mechanics is assumed within each metabasin, and the intermetabasin dynamics are computed using a reduced set of master equations. The number of metabasins depends upon both the temperature of the system and its derivative with respect to time. With this technique, the integration time step of the master equations is governed by the observation time scale rather than the fastest transition time between basins. We illustrate the technique using a simple model landscape with seven basins and show validation against direct Euler integration. Finally, we demonstrate the use of the technique for a realistic glass-forming system (viz., selenium) where direct Euler integration is not computationally feasible.

Original languageEnglish (US)
Pages (from-to)7957-7965
Number of pages9
JournalJournal of Physical Chemistry A
Volume111
Issue number32
DOIs
StatePublished - Aug 16 2007

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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