Free-volume origin of diverging direct correlations in hard crystals: insights from an exact one-dimensional model

Abstract

Second order direct correlation functions in three-dimensional hard-sphere crystals have much larger amplitudes (of the order of $1/n_{\mathrm{vac}}$ where $n_{\mathrm{vac}}$ is the vacancy concentration) and a more strongly structured spatial form of apparent shorter range than their liquid-state counterparts. We separate the two underlying questions---why the correlations are large and why they have the form they do---using the exact one-dimensional Percus functional for hard rods. A periodic crystal-like density is represented by Gaussian peaks with occupation probability $q=1-n_{\mathrm{vac}}$. The relevant thermodynamic quantity is the local insertion free volume $A(x)$. Its minimum can be written as $A_{\mathrm{min}} =\Delta_{\alpha a}+(1-\Delta_{\alpha a})n_{\mathrm{vac}}$, where $\Delta_{\alpha a}$ is the residual free volume at full occupation caused by finite localization (characterized by a width parameter $\alpha$) and lattice spacing $a$. The first and second direct correlations therefore contain the singular dependences $c^{(1)}\sim\ln A_{\mathrm{min}} $ and $c^{(2)} \sim-1/A_{\mathrm{min}} $. The observed $1/n_{\mathrm{vac}}$ dependence is the vacancy-dominated limit $n_{\mathrm{vac}}\gg\Delta_{\alpha a}$, rather than the most general result. The spatial form of $c^{(2)}$ has a separate geometrical origin: the hard-rod weight functions select configurations in which exclusion intervals and their boundaries intersect regions of small free volume. This produces plateaus, edges, and localized ridges tied to the underlying periodic density. A numerical solution of the inhomogeneous Ornstein--Zernike equation shows how these singular direct correlations are redistributed in the total and pair correlations. The model provides a minimal free-volume explanation for both the magnitude and the lattice-specific form of crystalline direct correlation functions.