Static, dynamic and electronic properties of expanded fluid mercury in the metal–nonmetal transition range. An abinitio study

Abstract

Fluid Hg undergoes a metal–nonmetal (M–NM) transition when expanded toward a density of around 9 g cm−3. We have performed ab initio molecular dynamics simulations for several thermodynamic states around the M–NM transition range and the associated static, dynamic and electronic properties have been analyzed. The calculated static structure shows a good agreement with the available experimental data. It is found that the volume expansion decreases the number of nearest neighbors from 10 (near the triple point) to around 8 at the M–NM transition region. Moreover, these neighbors are arranged into two subshells and the decrease in the number of neighbors occurs in the inner subshell. The calculated dynamic structure factors agree fairly well with their experimental counterparts obtained by inelastic x-ray scattering experiments, which display inelastic side peaks. The derived dispersion relation exhibits some positive dispersion for all the states, although its value around the M–NM transition region is not as marked as suggested by the experiment. We have also calculated the electronic density of states, which shows the appearance of a gap at a density of around 8.3 g cm−3.