Density-Dependent Analysis of Nonequilibrium Paths Improves Free Energy Estimates
arXiv:0901.3369 · doi:10.1063/1.3139189
Abstract
When a system is driven out of equilibrium by a time-dependent protocol that modifies the Hamiltonian, it follows a nonequilibrium path. Samples of these paths can be used in nonequilibrium work theorems to estimate equilibrium quantities, such as free energy differences. Here, we consider analyzing paths generated with one protocol using another one. It is posited that analysis protocols which minimize the lag, the difference between the nonequilibrium and the instantaneous equilibrium densities, will reduce the dissipation of reprocessed trajectories and lead to better free energy estimates. Indeed, when minimal lag analysis protocols based on exactly soluble propagators or relative entropies are applied to several test cases, substantial gains in the accuracy and precision of estimated free energy differences are observed.
12 pages, 6 figures. Expanded and clarified from original version. To appear in J. Chem. Phys
References in corpus (15)
- A nonequilibrium equality for free energy differences
- The Entropy Production Fluctuation Theorem and the Nonequilibrium Work Relation for Free Energy Differences
- Equilibrium free energy differences from nonequilibrium measurements: a master equation approach
- Verification of the Crooks fluctuation theorem and recovery of RNA folding free energies
- Path ensembles averages in systems driven far-from-equilibrium
- Optimal finite-time processes in stochastic thermodynamics
- Rare events and the convergence of exponentially averaged work values
- Theory of Systematic Computational Error in Free Energy Differences
- Optimal protocols for minimal work processes in underdamped stochastic thermodynamics
- Escorted Free Energy Simulations: Improving Convergence by Reducing Dissipation
- Single-ensemble nonequilibrium path-sampling estimates of free energy differences
- Computing the optimal protocol for finite-time processes in stochastic thermodynamics
- Bayesian estimates of free energies from nonequilibrium work data in the presence of instrument noise
- Path integral analysis of Jarzynski's equality: Analytical results
- Optimum bias for fast-switching free energy calculations