A theory of solid solutions and solid-fluid equilibria for mixtures

Abstract

We describe the application of a recently developed cell theory of solid solutions to the calculation of solid phase thermodynamics and solid-fluid phase eqt, ilibria for hard sphere mixtures. We focus on freezing into both substitutionally ordered and substitutionally disordered solid solutions. A comparison with Monte Carlo simulation results is presented.

Lattice-switch Monte Carlo simulation for binary hard-sphere crystals

“…The lattice switch results are in clear agreement with the results determined via integration methods [6,7], and with the DFT results presented in [30] and the cell theory results in [29]. For clarity, Figure 6 only includes the results presented in [6,7] and omits the almost identical results of [28,29]. The excess (i.e.…”

“…Theoretical studies of AB2, AB13 & AB(CsCl) have been also carried out via cell theory [28,29], and density functional theory (DFT) [30,31,32]. For AB2 and AB13, the results are generally consistent with both the integration method and experimental results, although some minor differences remain.…”

“…The basic approach has been presented in [27] by Bartlett, who considered only the fluid and pure (face-centered cubic A or B) crystal phases. We shall follow the work of Eldridge et al [5,6,7,20] and Cottin and Monson [28,29] and also include AB2, AB13 and AB(CsCl) as candidate two-component crystals. In the Eldridge [5] work, the stability of AB2 and AB13 for binary hard spheres was determined using the thermodynamic integration method of Frenkel and Ladd [4], with further details of the AB2 calculations in [6] and AB13 in [7].…”

Molecular Modeling of Solid Fluid Phase Behavior

“…We developed a theory of the free energy of for solid phase binary mixtures based on the cell theory [10][11][12][13]15]. The theory was applied to hard sphere mixtures and to Lennard-Jones 12-6 mixtures and gave predictions that were generally superior to those from other methods.…”