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A central endeavor of thermodynamics is the measurement of free energy changes. Regrettably, although we can measure the free energy of a system in thermodynamic equilibrium, typically all we can say about the free energy of a…

Statistical Mechanics · Physics 2012-04-10 David A. Sivak , Gavin E. Crooks

We study a class of non-equilibrium quasi-stationary states for a Markov system interacting with two different thermal baths. We show that the work done under a slow, external change of parameters admits a potential, i.e., the free energy.…

Statistical Mechanics · Physics 2017-05-23 A. E. Allahverdyan , N. H. Martirosyan

We develop a systematic procedure to approximate generalized free energy in out of equilibrium stochastic systems. The procedure only requires knowledge of the averages of macroscopic observables and uses quasi-equilibrium distribution to…

Disordered Systems and Neural Networks · Physics 2013-09-05 Alexander Mozeika

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…

Statistical Mechanics · Physics 2009-11-11 Paul Maragakis , Martin Spichty , Martin Karplus

According to the Jarzynski theorem, equilibrium free energy differences can be calculated from the statistics of work carried out during non-equilibrium transformations. Although exact, this approach can be plagued by large statistical…

Statistical Mechanics · Physics 2007-05-23 Wolfgang Lechner , Christoph Dellago

We study continuity, and lack thereof, of thermodynamical properties for one-dimensional dynamical systems. Under quite general hypotheses, the free energy is shown to be almost upper-semicontinuous: some normalised component of a limit…

Dynamical Systems · Mathematics 2020-03-13 Neil Dobbs , Mike Todd

It has recently been shown that the Helmholtz free energy difference between two equilibrium configurations of a system may be obtained from an ensemble of finite-time (nonequilibrium) measurements of the work performed in switching an…

Statistical Mechanics · Physics 2009-10-30 C. Jarzynski

A recent result, relating the (irreversible) work performed on a system during a non-quasistatic process, to the Helmholtz free energy difference between two equilibrium states of the system, is discussed. A proof of this result is given…

Statistical Mechanics · Physics 2007-05-23 C. Jarzynski

Starting for the Stillinger and Weber expression for the free energy of supercooled liquids, we extend the free energy to the case in which two time scales separate and the system is in quasi-equilibrium. The concept of an effective…

Soft Condensed Matter · Physics 2012-11-26 Antonio Scala , Francesco Sciortino

In this work, I propose a statistical mechanical framework, for the evaluation of the free energy in molecular systems, by "deleting" all the molecules in a "single" step. The approach can be considered as the statistical mechanics…

Statistical Mechanics · Physics 2011-08-16 Georgios C. Boulougouris

This article describes nonequilibrium techniques for the calculation of free energies of solids using molecular dynamics (MD) simulations. These methods provide an alternative to standard equilibrium thermodynamic integration methods and…

Materials Science · Physics 2022-01-13 Rodrigo Freitas , Mark Asta , Maurice de Koning

We devise automated workflows for the calculation of Helmholtz and Gibbs free energies and their temperature and pressure dependence and provide the corresponding computational tools. We employ non-equilibrium thermodynamics for evaluating…

Materials Science · Physics 2021-10-13 Sarath Menon , Yury Lysogorskiy , Jutta Rogal , Ralf Drautz

Chemical processes in closed systems are poorly controllable since they always relax to equilibrium. Living systems avoid this fate and give rise to a much richer diversity of phenomena by operating under nonequilibrium conditions. Recent…

Chemical Physics · Physics 2019-09-11 Emanuele Penocchio , Riccardo Rao , Massimiliano Esposito

Calculating free energy differences is a topic of substantial interest and has many applications including molecular docking and hydration, solvation, and binding free energies which is used in computational drug discovery. However, in…

Chemical Physics · Physics 2013-10-16 Asaf Farhi

Estimating the free energy in molecular simulation requires, implicitly or explicitly, counting how many times the system is observed in a finite region. If the simulation is biased by an external potential, the weight of the configurations…

Chemical Physics · Physics 2021-12-22 Matteo Carli , Alessandro Laio

An expression is derived for the classical free energy difference between two configurations of a system, in terms of an ensemble of finite-time measurements of the work performed in parametrically switching from one configuration to the…

Statistical Mechanics · Physics 2009-10-28 C. Jarzynski

An open question in the field of non-equilibrium statistical physics is whether there exists a unique way through which non-equilibrium systems equilibrate irrespective of how far they are away from equilibrium. To answer this question we…

Statistical Mechanics · Physics 2014-03-14 P. Barat , A. Giri , Nilangshu K. Das , M. Bhattacharya , A. Dutta

Recent years have witnessed major advances in our understanding of nonequilibrium processes. The Jarzynski equality, for example, provides a link between equilibrium free energy differences and finite-time, nonequilibrium dynamics. We…

Statistical Mechanics · Physics 2016-04-27 Dibyendu Mandal , Michael R. DeWeese

In this paper, we review the physical concepts of the nonequilibrium techniques for the calculation of free energies applied to magnetic systems using Monte Carlo simulations of different nonequilibrium processes. The methodology allows the…

Statistical Mechanics · Physics 2019-05-01 Samuel Cajahuaringa , Alex Antonelli

There are only a very few known relations in statistical dynamics that are valid for systems driven arbitrarily far-from-equilibrium. One of these is the fluctuation theorem, which places conditions on the entropy production probability…

Statistical Mechanics · Physics 2009-09-25 Gavin E. Crooks
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