Exploration of effective potential landscapes using coarse reverse integration

J Chem Phys. 2009 Oct 7;131(13):134104. doi: 10.1063/1.3207882.

Abstract

We describe a reverse integration approach for the exploration of low-dimensional effective potential landscapes. Coarse reverse integration initialized on a ring of coarse states enables efficient navigation on the landscape terrain: Escape from local effective potential wells, detection of saddle points, and identification of significant transition paths between wells. We consider several distinct ring evolution modes: Backward stepping in time, solution arc length, and effective potential. The performance of these approaches is illustrated for a deterministic problem where the energy landscape is known explicitly. Reverse ring integration is then applied to noisy problems where the ring integration routine serves as an outer wrapper around a forward-in-time inner simulator. Two versions of such inner simulators are considered: A Gillespie-type stochastic simulator and a molecular dynamics simulator. In these "equation-free" computational illustrations, estimation techniques are applied to the results of short bursts of inner simulation to obtain the unavailable (in closed-form) quantities (local drift and diffusion coefficient estimates) required for reverse ring integration; this naturally leads to approximations of the effective landscape.

Publication types

  • Research Support, N.I.H., Intramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Algorithms*
  • Dipeptides / chemistry
  • Molecular Conformation
  • Molecular Dynamics Simulation*
  • Thermodynamics
  • Water / chemistry

Substances

  • Dipeptides
  • Water
  • alanylalanine