Microcanonical calculations of excess thermodynamic properties of dense binary systems.

Abstract

We derive a formulation to calculate the excess chemical potential of a fraction of N1 particles interacting with N2 particles of a different species. The excess chemical potential is calculated numerically from first principles by coupling molecular dynamics and Thomas-Fermi density functional theory to take into account the contribution arising from the quantum electrons on the forces acting on the ions. The choice of this simple functional is motivated by the fact that the present paper is devoted to the derivation and the validation of the method but more complicated functionals can and will be implemented in the future. This method is applied in the microcanonical ensemble, the most natural ensemble for molecular dynamics simulations. This avoids the introduction of a thermostat in the simulation and thus uncontrolled modifications of the trajectories calculated from the forces between particles. The calculations are conducted for three values of the input thermodynamic quantities, energy and density, and for different total numbers of particles in order to examine the uncertainties due to finite-size effects. This method and these calculations lie the basic foundation to study the thermodynamic stability of dense mixtures, without any a priori assumption on the degree of ionization of the different species.