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J Chem Phys. 2009 Oct 7;131(13):134110. doi: 10.1063/1.3242285.

Optimal estimators and asymptotic variances for nonequilibrium path-ensemble averages.

Author information

1
Laboratory of Chemical Physics, NIDDK, National Institutes of Health, Bethesda, Maryland 20892, USA. daveminh@gmail.com

Abstract

Existing optimal estimators of nonequilibrium path-ensemble averages are shown to fall within the framework of extended bridge sampling. Using this framework, we derive a general minimal-variance estimator that can combine nonequilibrium trajectory data sampled from multiple path-ensembles to estimate arbitrary functions of nonequilibrium expectations. The framework is also applied to obtain asymptotic variance estimates, which are a useful measure of statistical uncertainty. In particular, we develop asymptotic variance estimates pertaining to Jarzynski's equality for free energies and the Hummer-Szabo expressions for the potential of mean force, calculated from uni- or bidirectional path samples. These estimators are demonstrated on a model single-molecule pulling experiment. In these simulations, the asymptotic variance expression is found to accurately characterize the confidence intervals around estimators when the bias is small. Hence, the confidence intervals are inaccurately described for unidirectional estimates with large bias, but for this model it largely reflects the true error in a bidirectional estimator derived by Minh and Adib.

PMID:
19814546
PMCID:
PMC2771048
DOI:
10.1063/1.3242285
[Indexed for MEDLINE]
Free PMC Article

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