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Molecular dynamics is a powerful tool for studying the thermodynamics and kinetics of complex molecular events. However, these simulations can rarely sample the required time scales in practice. Transition path sampling overcomes this…

Chemical Physics · Physics 2023-07-31 Gianmarco Lazzeri , Hendrik Jung , Peter G. Bolhuis , Roberto Covino

The accurate estimation of free energy differences between two states is a long-standing challenge in molecular simulations. Traditional approaches generally rely on sampling multiple intermediate states to ensure sufficient overlap in…

Statistical Mechanics · Physics 2026-03-17 Maximilian Schebek , Jiajun He , Emil Hoffmann , Yuanqi Du , Frank Noé , Jutta Rogal

Alchemical free energy calculations are a useful tool for predicting free energy differences associated with the transfer of molecules from one environment to another. The hallmark of these methods is the use of "bridging" potential energy…

In this paper we study theoretically the process of electron capture between one-optical-electron atoms (e.g. hydrogenlike or alkali atoms) and ions at low-to-medium impact velocities ($v/v_e \approx 1$) working on a modification of an…

Atomic Physics · Physics 2009-11-07 F. Sattin

A powerful and well-established tool for free-energy estimation is Bennett's acceptance ratio method. Central properties of this estimator, which employs samples of work values of a forward and its time reversed process, are known: for…

Statistical Mechanics · Physics 2009-09-16 Aljoscha Maria Hahn , Holger Then

The nonequilibrium fluctuation theorems have paved the way for estimating equilibrium thermodynamic properties, such as free energy differences, using trajectories from driven nonequilibrium processes. While many statistical estimators may…

Statistical Mechanics · Physics 2012-08-27 David D. L. Minh , Suriyanarayanan Vaikuntanathan

Many enhanced sampling techniques rely on the identification of a number of collective variables that describe all the slow modes of the system. By constructing a bias potential in this reduced space one is then able to sample efficiently…

Computational Physics · Physics 2019-03-05 Michele Invernizzi , Michele Parrinello

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

Different computational techniques in combination with molecular dynamics computer simulation are used to to determine the wall-liquid and the wall-crystal interfacial free energies of a modified Lennard-Jones (LJ) system in contact with a…

Statistical Mechanics · Physics 2015-06-16 Ronald Benjamin , Jürgen Horbach

We show how thermodynamic properties of molecular models can be computed over a large, multidimensional parameter space by combining multistate reweighting analysis with a linear basis function approach. This approach reduces the…

Chemical Physics · Physics 2016-05-18 Levi N. Naden , Michael R. Shirts

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

The binomial acceptance correction procedure is studied for particle number distributions detected in high energy reactions in finite regions of the momentum space. We present acceptance correction formulas for scaled variance, skewness,…

High Energy Physics - Phenomenology · Physics 2020-03-25 Oleh Savchuk , Roman V. Poberezhnyuk , Volodymyr Vovchenko , Mark I. Gorenstein

For a wide class of Hamiltonians, a novel method to obtain lower and upper bounds for the lowest energy is presented. Unlike perturbative or variational techniques, this method does not involve the computation of any integral (a…

Quantum Physics · Physics 2009-11-10 Amaury Mouchet

Free energies play a central role in characterising the behaviour of chemical systems and are among the most important quantities that can be calculated by molecular dynamics simulations. Solvation free energies in various organic solvents,…

Chemical Physics · Physics 2026-02-11 J. Harry Moore , Daniel J. Cole , Gabor Csanyi

We make the case for studying the complexity of approximately simulating (sampling) quantum systems for reasons beyond that of quantum computational supremacy, such as diagnosing phase transitions. We consider the sampling complexity as a…

Quantum Physics · Physics 2018-08-07 Abhinav Deshpande , Bill Fefferman , Minh C. Tran , Michael Foss-Feig , Alexey V. Gorshkov

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 consider energy absorption in an externally driven complex system of noninteracting fermions with the chaotic underlying dynamics described by the unitary random matrices. In the absence of quantum interference the energy absorption rate…

Mesoscale and Nanoscale Physics · Physics 2009-11-10 M. A. Skvortsov , D. M. Basko , V. E. Kravtsov

We present a method for computing free-energy differences using thermodynamic integration with a neural network potential that interpolates between two target Hamiltonians. The interpolation is defined at the sample distribution level, and…

Statistical Mechanics · Physics 2025-03-26 Bálint Máté , François Fleuret , Tristan Bereau

We describe a novel algorithm that learns a Hamiltonian from local expectations of its Gibbs state using the free energy variational principle. The algorithm avoids the need to compute the free energy directly, instead using efficient…

Quantum Physics · Physics 2024-09-25 Adam Artymowicz

Free energy profile (FE Profile) is an essential quantity for the estimation of reaction rate and the validation of reaction mechanism. For chemical reactions in condensed phase or enzymatic reactions, the computation of FE profile at ab…

Computational Physics · Physics 2018-11-15 Pengfei Li , Xiangyu Jia , Xiaoliang Pan , Yihan Shao , Ye Mei