Escorted Free Energy Simulations: Improving Convergence by Reducing Dissipation

Abstract

Nonequilibrium, ``fast switching'' estimates of equilibrium free energy differences, Delta F, are often plagued by poor convergence due to dissipation. We propose a method to improve these estimates by generating trajectories with reduced dissipation. Introducing an artificial flow field that couples the system coordinates to the external parameter driving the simulation, we derive an identity for Delta F in terms of the resulting trajectories. When the flow field effectively escorts the system along a near-equilibrium path, the free energy estimate converges efficiently and accurately. We illustrate our method on a model system, and discuss the general applicability of our approach.

4 pages, including 2 figures, accepted for publication in Phys Rev Lett

References in corpus (13)

• 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
• 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
• A "fast growth" method of computing free energy differences
• Targeted free energy perturbation
• Single-ensemble nonequilibrium path-sampling estimates of free energy differences
• Work probability distribution in systems driven out of equilibrium
• Equilibrium free energies from fast-switching trajectories with large time steps
• Entropy and density of states from isoenergetic nonequilibrium processes
• Generating Generalized Distributions from Dynamical Simulation

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