Validity of compressibility equation and Kirkwood-Buff theory in crystalline matter

Abstract

Volume integrals over the radial pair-distribution function, so-called Kirkwood-Buff integrals (KBI) play a central role in the theory of solutions, by linking structural with thermodynamic information. The simplest example is the compressibility equation, a fundamental relation in statistical mechanics of fluids. Until now, KBI theory could not be applied to crystals, because the integrals strongly diverge when computed in the standard way. We solve the divergence problem and generalize KBI theory to crystalline matter by using the recently proposed finite-volume theory. For crystals with harmonic interaction, we derive an analytic expression for the peak shape of the pair-distribution function at finite temperature. From this we demonstrate that the compressibility equation holds exactly in harmonic crystals.

5 pages, 4 figures. Accepted in Phys. Rev. E (Letter) on 10 May 2021. https://journals.aps.org/pre/accepted/5c07aY10N5a15971027002e9cbb161c323fec3129

References in corpus (1)

• Ensemble averaged Madelung energies of finite volumes and surfaces

Cited by in corpus (1)

• Connecting density fluctuations and Kirkwood-Buff integrals for finite-size systems