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Non‐Boltzmann sampling and Bennett's acceptance ratio method: How to profit from bending the rules
Author(s) -
König Gerhard,
Boresch Stefan
Publication year - 2010
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21687
Subject(s) - sampling (signal processing) , computation , computer science , boltzmann constant , energy (signal processing) , mathematical optimization , umbrella sampling , process (computing) , statistical physics , mathematics , algorithm , statistics , molecular dynamics , chemistry , computational chemistry , physics , thermodynamics , filter (signal processing) , computer vision , operating system
The exact computation of free energy differences requires adequate sampling of all relevant low energy conformations. Especially in systems with rugged energy surfaces, adequate sampling can only be achieved by biasing the exploration process, thus yielding non‐Boltzmann probability distributions. To obtain correct free energy differences from such simulations, it is necessary to account for the effects of the bias in the postproduction analysis. We demonstrate that this can be accomplished quite simply with a slight modification of Bennett's Acceptance Ratio method, referring to this technique as Non‐Boltzmann Bennett. We illustrate the method by several examples and show how a creative choice of the biased state(s) used during sampling can also improve the efficiency of free energy simulations. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011