Force density functional theory in- and out-of-equilibrium

TL;DR

This paper develops a force density functional theory based on two-body correlations to describe inhomogeneous classical fluids, providing an alternative to standard potential-based density functional theory for equilibrium and out-of-equilibrium systems.

Contribution

It introduces a force-based density functional framework explicitly using two-body correlations, offering new insights into inhomogeneous fluid microstructure and force balance.

Findings

Force-based profiles align with virial pressure in equilibrium.

Standard DFT profiles are consistent with compressibility pressure.

The theory offers deep insights into correlations in dense systems.

Abstract

When a fluid is subject to an external field, as is the case near an interface or under spatial confinement, then the density becomes spatially inhomogeneous. Although the one-body density provides much useful information, a higher level of resolution is provided by the two-body correlations. These give a statistical description of the internal microstructure of the fluid and enable calculation of the average interparticle force, which plays an essential role in determining both the equilibrium and dynamic properties of interacting fluids. We present a theoretical framework for the description of inhomogeneous (classical) many-body systems, based explicitly on the two-body correlation functions. By consideration of local Noether-invariance against spatial distortion of the system we demonstrate the fundamental status of the Yvon-Born-Green (YBG) equation as a local force-balance within the fluid. Using the inhomogeneous Ornstein-Zernike equation we show that the two-body correlations are density functionals and, thus, that the average interparticle force entering the YBG equation is also a functional of the one-body density. The force-based theory we develop provides an alternative to standard density functional theory for the study of inhomogeneous systems both in- and out-of-equilibrium. We compare force-based density profiles to the results of the standard potential-based (dynamical) density functional theory. In equilibrium, we confirm both analytically and numerically that the standard approach yields profiles that are consistent with the compressibility pressure, whereas the force-density functional gives profiles consistent with the virial pressure. The structure of the theory offers deep insights into the nature of correlation in dense and inhomogeneous systems.