Measuring the convergence of Monte Carlo free energy calculations
arXiv:0910.2858 · doi:10.1103/PhysRevE.81.041117
Abstract
The nonequilibrium work fluctuation theorem provides the way for calculations of (equilibrium) free energy based on work measurements of nonequilibrium, finite-time processes and their reversed counterparts by applying Bennett's acceptance ratio method. A nice property of this method is that each free energy estimate readily yields an estimate of the asymptotic mean square error. Assuming convergence, it is easy to specify the uncertainty of the results. However, sample sizes have often to be balanced with respect to experimental or computational limitations and the question arises whether available samples of work values are sufficiently large in order to ensure convergence. Here, we propose a convergence measure for the two-sided free energy estimator and characterize some of its properties, explain how it works, and test its statistical behavior. In total, we derive a convergence criterion for Bennett's acceptance ratio method.
14 pages, 17 figures
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Cited by in corpus (3)
- Colloquium. Quantum Fluctuation Relations: Foundations and Applications
- Escorted free energy simulations
- Estimating equilibrium ensemble averages using multiple time slices from driven nonequilibrium processes: theory and application to free energies, moments, and thermodynamic length in single-molecule pulling experiments