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We present an approach to the estimate of the potential of mean force along ageneric reaction coordinate based on maximum likelihood methods andpath-ensemble averages in systems driven far from equilibrium. Followingsimilar arguments, various free energy estimators can be recovered, allproviding comparable computational accuracy. The method, applied to theunfolding process of the alpha-helix form of an alanine deca-peptide, givesresults in good agreement with thermodynamic integration.

Calculation of the potential of mean force from nonequilibrium measurements via maximum likelihood estimators