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A critical challenge for density functional theory (DFT) in practice is its limited ability to treat static electron correlation, leading to errors in its prediction of charges, multiradicals, and reaction barriers. Recently, we combined…

Chemical Physics · Physics 2024-11-05 Daniel Gibney , Jan-Niklas Boyn , David A. Mazziotti

We propose a generalisation of molecular density functional theory to describe inhomogeneous solvent mixture, with the objective of modelling electrolytic solutions. Two electrolytic models are presented, both within the HNC approximation.…

Chemical Physics · Physics 2025-11-13 Guillaume Jeanmairet , Luc Belloni , Daniel Borgis

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

Due to efficient scaling with electron number N, density functional theory (DFT) is widely used for studies of large molecules and solids. Restriction of an exact mean-field theory to local potential functions has recently been questioned.…

Other Condensed Matter · Physics 2015-06-24 Robert K. Nesbet

We study the behavior of very thin liquid films wetting homogeneous planar and spherical substrates. In order to describe a simple fluid at very small scales, we employ a classical density functional theory (DFT). Here, we model a fluid…

Statistical Mechanics · Physics 2017-01-10 Andreas Nold

On a basis of a two-length scale description of hydrophobic interactions we develop a continuous self-consistent theory of solute-water interactions which allows to determine a hydrophobic layer of a solute molecules of any geometry with…

Soft Condensed Matter · Physics 2007-05-23 G. Sitnikov , S. Nechaev , M. Taran , A. Muryshev

Linear-scaling implementations of density functional theory (DFT) reach their intended efficiency regime only when applied to systems having a physical size larger than the range of their Kohn-Sham density matrix (DM). This causes a problem…

Chemical Physics · Physics 2022-03-25 Marcel David Fabian , Ben Shpiro , Eran Rabani , Daniel Neuhauser , Roi Baer

Classical density functional theory (cDFT) provides a systematic approach to predict the structure and thermodynamic properties of chemical systems through the single-molecule density profiles. Whereas the statistical-mechanical framework…

Chemical Physics · Physics 2024-11-07 Jinni Yang , Runtong Pan , Jikai Sun , Jianzhong Wu

Classical Density Functional Theory (DFT) is a statistical-mechanical framework to analyze fluids, which accounts for nanoscale fluid inhomogeneities and non-local intermolecular interactions. DFT can be applied to a wide range of…

Computational Engineering, Finance, and Science · Computer Science 2017-02-07 Andreas Nold , Benjamin D. Goddard , Peter Yatsyshin , Nikos Savva , Serafim Kalliadasis

A comprehensive, semi-quantitative model for the thermodynamics of hydrophobic solvation is presented. The model is based on a very simple premise suggested by the scaled particle theory and treats both solute and solvent molecules as hard…

Biological Physics · Physics 2007-05-23 Hong Qian

Previously, it has been shown that the direct correlation function for a Lennard-Jones fluid could be modeled by a sum of that for hard-spheres, a mean-field tail and a simple linear correction in the core region constructed so as to…

Statistical Mechanics · Physics 2008-08-20 James F. Lutsko

Although the classical density functional theory (DFT) of inhomogeneous fluids was formulated more than four decades ago, its application to broken symmetry phases of molecular systems remained a challenge. Approximate free energy…

Statistical Mechanics · Physics 2026-05-19 Yashwant Singh

Using a hydrogen molecule as a test system we demonstrate how to compute the effective potential according to the formalism of the new density functional theory (DFT), in which the basic variable is the set of spherically averaged densities…

Chemical Physics · Physics 2020-09-22 K. Kokko , Á. Nagy , J. Huhtala , T. Björkman , L. Vitos

The structure of dilute electrolyte solutions close to a surface carrying a spatially inhomogeneous surface charge distribution is investigated by means of classical density functional theory (DFT) within the approach of fundamental measure…

Soft Condensed Matter · Physics 2020-06-23 Maximilian Mußotter , Markus Bier , S. Dietrich

Orbital-free density functional theory (OF-DFT) provides an alternative approach for calculating the molecular electronic energy, relying solely on the electron density. In OF-DFT, both the ground-state density is optimized variationally to…

Chemical Physics · Physics 2023-11-23 Alexandre de Camargo , Ricky T. Q. Chen , Rodrigo A. Vargas-Hernández

Describing analytically the transport properties of electrolytes, such as their conductivity or the self-diffusion of the ions, has been a central challenge of chemical physics for almost a century. In recent years, this question has…

Soft Condensed Matter · Physics 2023-09-21 Olivier Bernard , Marie Jardat , Benjamin Rotenberg , Pierre Illien

Density-corrected density functional theory (DC-DFT) is enjoying substantial success in improving semilocal DFT calculations in a wide variety of chemical problems. This paper provides the formal theoretical framework and assumptions for…

Chemical Physics · Physics 2019-08-19 Stefan Vuckovic , Suhwan Song , John Kozlowski , Eunji Sim , Kieron Burke

In recent years, the theoretical description of electrical noise and fluctuation-induced effects in electrolytes has gained a renewed interest, enabled by stochastic field theories like stochastic density functional theory (SDFT). Such…

Soft Condensed Matter · Physics 2025-03-25 Pierre Illien , Antoine Carof , Benjamin Rotenberg

The properties of a hard-sphere fluid in contact with hard spherical and cylindrical walls are studied. Rosenfeld's density functional theory (DFT) is applied to determine the density profile and surface tension $\gamma$ for wide ranges of…

Statistical Mechanics · Physics 2007-05-23 P. Bryk , R. Roth , K. R. Mecke , S. Dietrich

A density functional theory (DFT) framework is presented that links functional derivatives of free-energy functionals to non-linear static density response functions in quantum many-body systems. Within this framework, explicit expressions…