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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…

Statistical Mechanics · Physics 2010-04-26 Aljoscha M. Hahn , Holger Then

The estimate of free energy changes based on Bennett's acceptance ratio method is examined in several limiting cases and compared with other estimates based on the Jarzynski equality and on the Crooks relation. While the absolute amount of…

Statistical Mechanics · Physics 2015-06-12 Seongjin Kim , Yong Woon Kim , Peter Talkner , Juyeon Yi

The Jarzynski equality is one of the most influential results in the field of non equilibrium statistical mechanics. This celebrated equality allows to calculate equilibrium free energy differences from work distributions of nonequilibrium…

Statistical Mechanics · Physics 2017-09-13 Shahaf Asban , Saar Rahav

Free energy calculations based on atomistic Hamiltonians provide microscopic insight into the thermodynamic driving forces of biophysical or condensed matter systems. Many approaches use intermediate Hamiltonians interpolating between the…

Computational Physics · Physics 2021-12-08 Martin Reinhardt , Helmut Grubmüller

Free energy of crystal phases is commonly evaluated by thermodynamic integration (TDI) along a reversible path that involves an external potential. A persistent problem in this method is that a significant hysteresis is observed due to…

Materials Science · Physics 2010-02-27 Pankaj A. Apte

The multistate Bennett Acceptance Ratio is provably the lowest variance unbiased estimator of both free energies and ensemble averages, and has a number of important advantages over previous methods, such as WHAM. Despite its advantages,…

Statistical Mechanics · Physics 2017-12-20 Michael R. Shirts

Fast and accurate evaluation of free energy has broad applications from drug design to material engineering. Computing the absolute free energy is of particular interest since it allows the assessment of the relative stability between…

Statistical Mechanics · Physics 2021-02-24 Xinqiang Ding , Bin Zhang

A key ingredient in quantum resource theories is a notion of measure. Such as a measure should have a number of fundamental properties, and desirably also a clear operational meaning. Here we show that a natural measure known as the convex…

Quantum Physics · Physics 2020-09-16 Roope Uola , Tom Bullock , Tristan Kraft , Juha-Pekka Pellonpää , Nicolas Brunner

Free energy calculations based on atomistic Hamiltonians and sampling are key to a first principles understanding of biomolecular processes, material properties, and macromolecular chemistry. Here, we generalize the Free Energy Perturbation…

Computational Physics · Physics 2023-07-19 Martin Reinhardt , Helmut Grubmüller

Estimating the expected value of an observable appearing in a non-equilibrium stochastic process usually involves sampling. If the observable's variance is high, many samples are required. In contrast, we show that performing the same task…

Statistical Mechanics · Physics 2015-04-07 T. H. Johnson , T. J. Elliott , S. R. Clark , D. Jaksch

In QM/MM indirect free energy simulation, QM/MM corrections can be obtained from integration of partial derivatives of alchemical Hamiltonians or from perturbation-based estimators including free energy perturbation (FEP) and acceptance…

Chemical Physics · Physics 2018-10-05 Xiaohui Wang , Zhaoxi Sun

In this paper, we investigate the statistical convergence rate of a Bayesian low-rank tensor estimator. Our problem setting is the regression problem where a tensor structure underlying the data is estimated. This problem setting occurs in…

Machine Learning · Statistics 2014-08-14 Taiji Suzuki

Free-energy-based adaptive biasing methods, such as Metadynamics, the Adaptive Biasing Force (ABF) and their variants, are enhanced sampling algorithms widely used in molecular simulations. Although their efficiency has been empirically…

Probability · Mathematics 2026-01-29 Tony Lelièvre , Xuyang Lin , Pierre Monmarché

A general framework with a series of different methods is proposed to improve the estimate of convex function (or functional) values when only noisy observations of the true input are available. Technically, our methods catch the bias…

Methodology · Statistics 2022-09-15 Chao Ma , Lexing Ying

The transition between a regime in which thermodynamic relations apply only to ensembles of small systems coupled to a large environment and a regime in which they can be used to characterize individual macroscopic systems is analyzed in…

Statistical Mechanics · Physics 2015-05-30 Alberto Suárez , Robert Silbey , Irwin Oppenheim

We consider the problem of sampling a high dimensional multimodal target probability measure. We assume that a good proposal kernel to move only a subset of the degrees of freedoms (also known as collective variables) is known a priori.…

Statistical Mechanics · Physics 2025-02-07 Christoph Schönle , Marylou Gabrié , Tony Lelièvre , Gabriel Stoltz

We present a new estimator for computing free energy differences and thermodynamic expectations as well as their uncertainties from samples obtained from multiple equilibrium states via either simulation or experiment. The estimator, which…

Computational Physics · Physics 2011-12-06 Michael R. Shirts , John D. Chodera

The multistate Bennett acceptance ratio (MBAR) method is a prevalent approach for computing free energies of thermodynamic states. In this work, we introduce BayesMBAR, a Bayesian generalization of the MBAR method. By integrating…

Chemical Physics · Physics 2024-02-16 Xinqiang Ding

An energy-biased method to evaluate ensemble averages requiring test-particle insertion is presented. The method is based on biasing the sampling within the subdomains of the test-particle configurational space with energies smaller than a…

Chemical Physics · Physics 2009-11-11 R. Delgado-Buscalioni , G. De Fabritiis , P. V. Coveney

We introduce a simple enhanced sampling approach for the calculation of free energy differences and barriers along a one-dimensional reaction coordinate. First, a small number of short nonequilibrium simulations are carried out along the…

Chemical Physics · Physics 2021-11-03 Kristof M. Bal
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