Integrating diffusion maps with umbrella sampling: Application to alanine dipeptide

Andrew L. Ferguson, Athanassios Z. Panagiotopoulos, Pablo G. Debenedetti, Ioannis G. Kevrekidis

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48 Scopus citations

Abstract

Nonlinear dimensionality reduction techniques can be applied to molecular simulation trajectories to systematically extract a small number of variables with which to parametrize the important dynamical motions of the system. For molecular systems exhibiting free energy barriers exceeding a few k BT, inadequate sampling of the barrier regions between stable or metastable basins can lead to a poor global characterization of the free energy landscape. We present an adaptation of a nonlinear dimensionality reduction technique known as the diffusion map that extends its applicability to biased umbrella sampling simulation trajectories in which restraining potentials are employed to drive the system into high free energy regions and improve sampling of phase space. We then propose a bootstrapped approach to iteratively discover good low-dimensional parametrizations by interleaving successive rounds of umbrella sampling and diffusion mapping, and we illustrate the technique through a study of alanine dipeptide in explicit solvent.

Original languageEnglish (US)
Article number135103
JournalJournal of Chemical Physics
Volume134
Issue number13
DOIs
StatePublished - Apr 7 2011

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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