First-principles order-parameter theory of freezing

Abstract

A first-principles order-parameter theory of the fluid-solid transition is presented in this paper. The thermodynamic potential Ω of the system is computed as a function of order parameters λ_i(=λ_k→i) proportional to the lattice periodic components of the one-particle density ρ(r→), K→_i's being the reciprocal-lattice vectors (RLV) of the crystal. Computation of Ω({λ_i}) is shown to require knowing Ω for a fluid placed in lattice periodic potentials with amplitudes depending on λ_i. Using systematic nonperturbative functional methods for calculating the response of the fluid to such potentials, we find Ω({λ_i}). The fluid properties (response functions) determining it are the Fourier coefficients c_i(=c_K→i) and c₀(=c_q→=0) of the direct correlation function c(r→). The system freezes when at constant chemical potential µ and pressure P, locally stable fluid and solid phases [i.e., minima of Ω({λ_i}) with {λ_i}=0 and {λ_i}≠0, respectively] have the same Ω. The order-parameter mode most effective in reducing Ω({λ_i}) corresponds to K→_j being of the smallest-length RLV set (c_q→ is largest for |q→|~=|K→_j|). In some cases one has to consider a second order parameter λ_n with a RLV K→_n lying near the second peak in c_q→. The effect of further order-parameter modes on Ω is shown to be small. The theory can be viewed as one of a strongly first-order density-wave phase transition in a dense classical system. The transition is a purely structural one, occurring when the fluid-phase structural correlations (measured by c_j, etc.) are strong enough. This fact has been brought out clearly by computer experiments but had not been theoretically understood so far. Calculations are presented for freezing into some simple crystal structures, i.e., fcc, bcc, and two-dimensional hcp. The input information is only the crystal structure and the fluid compressibility (related to c₀). We obtain as output the freezing criterion stated as a condition on c_j or as a relation between c_j and c_n, the volume change V, the entropy change Δs, and the Debye-Waller factor at freezing for various RLV values. The numbers are all in very good agreement with those available experimentally.