Study of theoretical models for the liquid-vapor and metal-nonmetal transitions of alkali fluids

TL;DR

This paper develops and tests a new statistical model for alkali fluid phase transitions, incorporating local environment effects and density fluctuations, with simulations matching experimental data.

Contribution

It introduces an inhomogeneous lattice-gas model with nonadditive interactions for alkali fluids, improving upon mean-field approaches.

Findings

Model accurately predicts phase transition properties of alkali fluids.

Monte Carlo simulations show good agreement with experimental data.

The approach captures structural, thermodynamic, and electronic behaviors.

Abstract

Theoretical models for the liquid-vapor and metal-nonmetal transitions of alkali fluids are investigated. Mean-field models are considered first but shown to be inadequate. An alternate approach is then studied in which each statistical configuration of the material is treated as inhomogeneous, with the energy of each ion being determined by its local environment. Nonadditive interactions, due to valence electron delocalization, are a crucial feature of the model. This alternate approach is implemented within a lattice-gas approximation which takes into account the observed mode of expansion in the materials of interest and which is able to treat the equilibrium density fluctuations. We have carried out grand canonical Monte Carlo simulations, for this model, which allow a unified, self-consistent, study of the structural, thermodynamic, and electronic properties of alkali fluids. Applications to Cs, Rb, K, and Na yield results in good agreement with observations.