Title
Bias and error in estimates of equilibrium free-energy differences from nonequilibrium measurements
Date Issued
28 October 2003
Access level
open access
Resource Type
journal article
Author(s)
University of California
Publisher(s)
National Academy of Sciences
Abstract
In 1997, Jarzynski proved a remarkable equality that allows one to compute the equilibrium free-energy difference ΔF between two states from the probability distribution of the nonequilibrium work W done on the system to switch between the states, e-ΔF/kT = 〈e -W/kT〉, [Jarzynski, C. (1997) Phys. Rev. Lett. 87, 2690-2693]. The Jarzynski equality provides a powerful free-energy difference estimator from a set of N irreversible experiments and is closely related to free-energy perturbation, a common computational technique for estimating free-energy differences. Despite the many applications of the Jarzynski estimator, its behavior is only poorly understood. In this article we derive the large N limit for the Jarzynski estimator bias, variance, and mean square error that is correct for arbitrary perturbations. We then analyze the properties of the Jarzynski estimator for all N when the probability distribution of work values is Gaussian, as occurs, for example, in the near-equilibrium regime. This allows us to quantitatively compare it to two other free-energy difference estimators: the mean work estimator and the fluctuation-dissipation theorem estimator. We show that, for near-equilibrium switching, the Jarzynski estimator is always superior to the mean work estimator and is even superior to the fluctuation-dissipation estimator for small N. The Jarzynski-estimator bias is shown to be the dominant source of error in many cases. Our expression for the bias is used to develop a bias-corrected Jarzynski free-energy difference estimator in the nearequilibrium regime.
Start page
12564
End page
12569
Volume
100
Issue
22
Language
English
OCDE Knowledge area
EstadÃsticas, Probabilidad
PsicologÃa
EconomÃa, Negocios
Scopus EID
2-s2.0-0242268467
PubMed ID
Source
Proceedings of the National Academy of Sciences of the United States of America
ISSN of the container
0027-8424
Sponsor(s)
National Institute of General Medical Sciences R37GM032543 NIGMS
Sources of information:
Directorio de Producción CientÃfica
Scopus