Optimal estimates of free energies from multistate nonequilibrium work data.
We derive the optimal estimates of the free energies of an arbitrary number of thermodynamic states from nonequilibrium work measurements; the work data are collected from forward and reverse switching processes and obey a fluctuation theorem. The maximum likelihood formulation properly reweights all pathways contributing to a free energy difference and is directly applicable to simulations and experiments. We demonstrate dramatic gains in efficiency by combining the analysis with parallel tempering simulations for alchemical mutations of model amino acids.
Maragakis
Paul
P
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
Spichty
Martin
M
Karplus
Martin
M
D000596:Amino Acids / Q000737:chemistry; D001703:Biophysics / Q000379:methods; D002627:Chemistry, Physical / Q000379:methods*; D004526:Efficiency; D019277:Entropy; D007700:Kinetics; D008956:Models, Chemical; D015233:Models, Statistical; D009154:Mutation; D010455:Peptides / Q000737:chemistry; D015203:Reproducibility of Results; D013816:Thermodynamics; D014937:Work
D000596:Amino Acids; D010455:Peptides