Density functional theory and the asymptotic high density expansion of the free energy of classical solids and fluids

1998/10/10 by YAAKOV ROSENFELD, Yaakov Rosenfeld, PEDRO TARAZONA +1 · 167 citations
Engineering · Materials Science · Mathematics · Physics and Astronomy · #Advanced Thermodynamics and Statistical Mechanics #Classical fluids #Classical mechanics #Density functional theory #Energy density #Hard spheres #Lattice (music) #Material Dynamics and Properties #Mathematical analysis #Mathematics #Perturbation theory (quantum mechanics) #Phase Equilibria and Thermodynamics #Physics #Quantum mechanics #Singularity #Theoretical physics #Thermodynamics

paper · doi:10.1080/00268979809483145

published in Molecular Physics 95(2), 141-150 (Taylor & Francis)

openalex publication_date 1998/10/10 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/29

Abstract

On the basis of the fundamental-measure free energy functional for hard spheres and thermodynamic perturbation theory, a unified analytical description of classical bulk solids and fluids is obtained, predicting correctly the major features of their equations of state and freezing parameters as obtained by simulations. The fundamentally different fluid and solid asymptotic high density expansions for the potential energy, featuring a static-lattice Madelung term and the harmonic 3/2k B T correction, on one hand, and a fluid Madelung energy with a ˜T 3/5 thermal energy correction, on the other, both originate from the same singularity in the hard sphere free energy functional.

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