Thermodynamic properties and phase equilibrium of fluid hydrogen from path integral simulations

Abstract

The thermodynamic properties of normal and para-hydrogen are computed from multiple time-step path integral hybrid Monte Carlo (PIHMC) simulations. Four different isotropic pair potentials are evaluated by comparing simulation results with experimental data. The Silvera–Goldman potential is found to be the most accurate of the potentials tested for computing the density and internal energy of fluid hydrogen. Using the Silvera–Goldman potential, simulation and experimental data are compared on isobars ranging from 0.1 to 100 MPa and for temperatures from 18 to 300 K. The Gibbs free energy is calculated from the PIHMC simulations by an adaptation of Widom's particle insertion technique to a path integral fluid. A new method is developed for computing phase equilibria for quantum fluids directly by combining PIHMC with the Gibbs ensemble technique. This Gibbs–PIHMC method is used to calculate the vapour–liquid phase diagram of hydrogen from simulations. Agreement with experimental data is good.