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We report here how the hydration of complex surfaces can be efficiently studied thanks to recent advances in classical molecular density functional theory. This is illustrated on the example of the pyrophylite clay. After presenting the…

Density functional theory (DFT) embedding provides a formally exact framework for interfacing correlated wave-function theory (WFT) methods with lower-level descriptions of electronic structure. Here, we report techniques to improve the…

Chemical Physics · Physics 2015-06-12 Jason D. Goodpaster , Taylor A. Barnes , Frederick R. Manby , Thomas F. Miller

Most of the performances of electrochemical devices are governed by molecular processes taking place at the solution-electrode interfaces and molecular simulation are the main way to study these processes. Aqueous electrochemical systems…

Chemical Physics · Physics 2019-12-12 Guillaume Jeanmairet , Benjamin Rotenberg , Daniel Borgis , Mathieu Salanne

Hard-sphere fluids confined between parallel plates a distance $D$ apart are studied for a wide range of packing fractions, including also the onset of crystallization, applying Monte Carlo simulation techniques and density functional…

Statistical Mechanics · Physics 2011-10-10 Debabrata Deb , Alexander Winkler , Mohammad Hossein Yamani , Martin Oettel , Peter Virnau , Kurt Binder

We introduce an approximation for the pair distribution function of the inhomogeneous hard sphere fluid. Our approximation makes use of our recently published averaged pair distribution function at contact which has been shown to accurately…

Soft Condensed Matter · Physics 2015-06-19 Paho Lurie-Gregg , Jeff B. Schulte , David Roundy

An accurate ab initio theory of the H-bond structure of liquid water requires a high-level exchange correlation approximation from density functional theory. Based on the liquid structures modeled by ab initio molecular dynamics by using…

Chemical Physics · Physics 2019-09-25 Jianhang Xu , Mohan Chen , Cui Zhang , Xifan Wu

We present and discuss some ideas concerning an ``average-pair-density functional theory'', in which the ground-state energy of a many-electron system is rewritten as a functional of the spherically and system-averaged pair density. These…

Materials Science · Physics 2009-11-11 Paola Gori-Giorgi , Andreas Savin

It has been extensively demonstrated through first principles quantum mechanics calculations that water exhibits strong hydrogen bond cooperativity. Classical molecular simulation and statistical mechanics methods typically assume pairwise…

Soft Condensed Matter · Physics 2017-05-24 Bennett D. Marshall

In this work, the solvation and electronic structure of the aqueous chloride ion solution was investigated using Density Functional Theory (DFT) based \textit{ab initio} molecular dynamics (AIMD). From an analysis of radial distribution…

The hydrogen-bond (H-bond) network of high-pressure water is investigated by neural-network-based molecular dynamics (MD) simulations with the first-principles accuracy. The static structure factors (SSFs) of water at three densities, i.e.,…

Chemical Physics · Physics 2023-08-04 Renxi Liu , Mohan Chen

A simple model is proposed for the direct correlation function (DCF) for simple fluids consisting of a hard-core contribution, a simple parametrized core correction, and a mean-field tail. The model requires as input only the free energy of…

Statistical Mechanics · Physics 2007-10-08 James F. Lutsko

A hard sphere fluid confined by hard, structureless, and parallel walls is investigated using a certain version of weighted density functional theory. The density profile, the excess coverage, the finite size contribution to the free…

Statistical Mechanics · Physics 2008-02-03 B. Gotzelmann , S. Dietrich

We use appropriately defined short ranged reference models of liquid water to clarify the different roles local hydrogen bonding, van der Waals attractions, and long ranged electrostatic interactions play in the solvation and association of…

Statistical Mechanics · Physics 2015-02-20 Richard C. Remsing , John D. Weeks

The fundamental measure approach to classical density functional theory has been shown to be a powerful tool to predict various thermodynamic properties of hard-sphere systems. We employ this approach to determine not only one-particle…

Soft Condensed Matter · Physics 2015-11-02 Andreas Härtel , Matthias Kohl , Michael Schmiedeberg

The role of solute attractive forces on hydrophobic interactions is studied by coordinated development of theory and simulation results for Ar atoms in water. We present a concise derivation of the local molecular field (LMF) theory for the…

Chemical Physics · Physics 2015-10-28 M. I. Chaudhari , S. B. Rempe , D. Asthagiri , L. Tan , L. R. Pratt

Classical density functional theory (DFT) is a powerful framework to study inhomogeneous fluids. Its standard form is based on the knowledge of a generating free energy functional. If this is known exactly, then the results obtained by…

Soft Condensed Matter · Physics 2025-05-02 S. M. Tschopp , H. Vahid , A. Sharma , J. M. Brader

More than half of a century has passed since the free energy of classical fluids defined by second Legendre transform was derived as a functional of density-density correlation function. It is now becoming an increasingly significant issue…

Statistical Mechanics · Physics 2018-12-05 Hiroshi Frusawa

Predicting the asymmetric structure and dynamics of solvated hydroxide and hydronium in water has been a challenging task from ab initio molecular dynamics (AIMD). The difficulty mainly comes from a lack of accurate and efficient…

Chemical Physics · Physics 2022-07-20 Renxi Liu , Chunyi Zhang , Xinyuan Liang , Jianchuan Liu , Xifan Wu , Mohan Chen

Quantum-chemical processes in liquid environments impact broad areas of science, from molecular biology to geology to electrochemistry. While density-functional theory (DFT) has enabled efficient quantum-mechanical calculations which…

Chemical Physics · Physics 2017-10-16 Kendra Letchworth-Weaver , Ravishankar Sundararaman , T. A. Arias

Site density functional theory (SDFT) provides a rigorous framework for statistical mechanics analysis of inhomogeneous molecular liquids. The key defining feature of these systems is the presence of two very distinct interactions scales…

Statistical Mechanics · Physics 2020-11-24 Gennady N. Chuev , Marina V. Fedotova , Marat Valiev