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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

We present a history-dependent Monte Carlo scheme for the efficient calculation of the free-energy of quantum systems, inspired by the Wang-Landau sampling and metadynamics method. When embedded in a path integral formulation, it is of…

Statistical Mechanics · Physics 2009-04-08 Yanier Crespo , Alessandro Laio , Giuseppe E. Santoro , Erio Tosatti

In quantum Monte Carlo (QMC) methods, energy estimators are calculated as the statistical average of the Markov chain sampling of energy estimator along with an associated statistical error. This error estimation is not straightforward and…

Computational Physics · Physics 2022-04-26 Tom Ichibha , Kenta Hongo , Ryo Maezono , Alex J. W. Thom

In this work the free energy of solid phases is computed for the Lennard-Jones potential and for a model of NaCl. The free energy is evaluated through the Einstein crystal/molecule methodologies using the Molecular Dynamics programs:…

Soft Condensed Matter · Physics 2012-10-16 J. L. Aragones , C. Valeriani , C. Vega

We present an \textit{ab initio} auxiliary field quantum Monte Carlo method for studying the electronic structure of molecules, solids, and model Hamiltonians at finite temperature. The algorithm marries the \textit{ab initio} phaseless…

Strongly Correlated Electrons · Physics 2018-11-13 Yuan Liu , Minsik Cho , Brenda Rubenstein

We propose an efficient method for Monte Carlo simulation of quantum lattice models. Unlike most other quantum Monte Carlo methods, a single run of the proposed method yields the free energy and the entropy with high precision for the whole…

Statistical Mechanics · Physics 2009-11-10 Chiaki Yamaguchi , Naoki Kawashima , Yutaka Okabe

In this thesis we examine methodologies for determining free energy differences (FEDs) of phases via Monte Carlo simulation. We identify and address three generic issues that arise in FED calculations; the choice of representation, the…

Statistical Mechanics · Physics 2009-09-29 Arjun R. Acharya

A simple technique is proposed for numerically determining equilibrium ion distribution functions belonging to free energies of the Poisson-Boltzmann type. The central idea is to perform a conventional Monte-Carlo simulation using the free…

Soft Condensed Matter · Physics 2009-10-31 Markus Deserno

Density matrix quantum Monte Carlo (DMQMC) is used to sample exact-on-average $N$-body density matrices for uniform electron gas systems of up to 10$^{124}$ matrix elements via a stochastic solution of the Bloch equation. The results of…

Strongly Correlated Electrons · Physics 2016-09-14 Fionn D. Malone , N. S. Blunt , Ethan W. Brown , D. K. K. Lee , J. S. Spencer , W. M. C. Foulkes , James J. Shepherd

We perform \emph{ab initio} quantum Monte Carlo (QMC) simulations of the warm dense uniform electron gas in the thermodynamic limit. By combining QMC data with linear response theory we are able to remove finite-size errors from the…

We present an elementary and self-contained account of the analogies existing between classical diffusion and the imaginary-time evolution of quantum systems. These analogies are used to develop a new quantum simulation method which allows…

Condensed Matter · Physics 2007-05-23 S. Baroni , S. Moroni

Free energy calculations in molecular simulations have a variety of applications including determining the strength of molecular processes such as solvation and binding. It has been recently shown that when removing the VDW and Coulomb…

Chemical Physics · Physics 2015-07-15 Asaf Farhi , Bipin Singh

Employing a classical density-functional description of liquid environments, we introduce a rigorous method for the diffusion quantum Monte Carlo calculation of free energies and thermodynamic averages of solvated systems that requires…

In this paper, I investigate more closely the recently proposed Free Energy Monte Carlo algorithm that is devised in particular for calculations where conventional Monte Carlo simulations struggle with ergodicity problems. The simplest…

Condensed Matter · Physics 2007-05-23 M. J. Thill

We introduce a new class of Sequential Monte Carlo (SMC) methods, which we call free energy SMC. This class is inspired by free energy methods, which originate from Physics, and where one samples from a biased distribution such that a given…

Computation · Statistics 2010-06-16 Nicolas Chopin , Pierre Jacob

Free energy sampling methods allow studying the full dynamics of activated processes. Unfortunately, the affordable accuracy of the potential describing the energy and forces of the system is usually rather low. Here we introduce a new…

Chemical Physics · Physics 2019-04-04 GiovanniMaria Piccini , Michele Parrinello

Free energies of molecules can be calculated by quantum computations or by normal mode classical calculations. However, the first can be computationally impractical for large molecules and the second is based on the assumption of harmonic…

Chemical Physics · Physics 2016-03-23 Asaf Farhi

Obtaining the free energies of condensed phase chemical reactions remains computationally prohibitive for high-level quantum mechanical methods. We introduce a hierarchical machine learning framework that bridges this gap by distilling…

Chemical Physics · Physics 2026-03-19 Chenghan Li , Garnet Kin-Lic Chan

Calculating relative free energies is a topic of substantial interest and has many applications including solvation and binding free energies, which are used in computational drug discovery. However, there remain the challenges of accuracy,…

Chemical Physics · Physics 2016-09-28 Asaf Farhi , Bipin Singh

We present a stable and systematically improvable quantum Monte Carlo (QMC) approach to calculating excited-state energies, which we implement using our fast randomized iteration method for the full configuration interaction problem…

Computational Physics · Physics 2023-10-03 Samuel M. Greene , Robert J. Webber , James E. T. Smith , Jonathan Weare , Timothy C. Berkelbach