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Improving Free-Energy Estimates from Unidirectional Work Measurements: Theory and Experiment
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We derive analytical expressions for the bias of the Jarzynski free-energy estimator from N nonequilibrium work measurements, for a generic work distribution. To achieve this, we map the estimator onto the random energy model in a suitable scaling limit parametrized by ( log N ) / μ , where μ measures the width of the lower tail of the work distribution, and then compute the finite- N corrections to this limit with different approaches for different regimes of ( log N ) / μ . We show that these expressions describe accurately the bias for a wide class of work distributions and exploit them to build an improved free-energy estimator from unidirectional work measurements. We apply the method to optical tweezers unfolding and refolding experiments on DNA hairpins of varying loop size and dissipation, displaying both near-Gaussian and non-Gaussian work distributions.
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PALASSINI, Matteo, RITORT FARRAN, Fèlix. Improving Free-Energy Estimates from Unidirectional Work Measurements: Theory and Experiment. _Physical Review Letters_. 2011. Vol. 107, núm. 6, pàgs. 060601. [consulta: 25 de gener de 2026]. ISSN: 0031-9007. [Disponible a: https://hdl.handle.net/2445/134467]