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Blue Moon Sampling, Vectorial Reaction Coordinates, and Unbiased Constrained Dynamics
Author(s) -
Ciccotti Giovanni,
Kapral Raymond,
VandenEijnden Eric
Publication year - 2005
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200400669
Subject(s) - scalar (mathematics) , reaction coordinate , sampling (signal processing) , dynamics (music) , molecular dynamics , conditional expectation , stochastic dynamics , perspective (graphical) , statistical physics , mathematics , physics , chemistry , computational chemistry , statistics , geometry , optics , detector , acoustics
We give a new formula expressing the components of the mean force in terms of a conditional expectation which can be computed by Blue Moon sampling. This generalizes to the vectorial case a formula first derived by Ruiz‐Montero et al. [ Mol. Phys. 1997 , 90 , 925] for a scalar reaction coordinate. We also discuss how to compute this conditional average by means of constrained stochastic dynamics which, unlike the usual constrained molecular dynamics, introduces no bias. Finally, we give a new perspective on bias removal by using constrained molecular dynamics.