title: Improving free-energy estimates from unidirectional work measurements: theory and experiment.
abstract: 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 (logN)/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 (logN)/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.
authors: Departament de Física Fonamental, Universitat de Barcelona, Spain.
authors: Matteo
authors: M
authors: Palassini
authors: Felix
authors: F
authors: Ritort
mesh_terms: D004247:DNA / Q000737:chemistry; D008962:Models, Theoretical; D016011:Normal Distribution; D009690:Nucleic Acid Conformation; D013816:Thermodynamics
chemical_list: D004247:DNA