Benchmarking vdW-DF first principle predictions against Coupled Electron-Ion Monte Carlo for high pressure liquid hydrogen

Abstract

We report first principle results for nuclear structure and optical responses of high pressure liquid hydrogen along two isotherms in the region of molecular dissociation. We employ Density Functional Theory with the vdW-DF approximation (vdW) and we benchmark the results against existing predictions from Coupling Electron-Ion Monte Carlo (CEIMC). At fixed density and temperature, we find that pressure from vdW is higher than pressure from CEIMC by about 10 GPa in the molecular insulating phase and about 20 GPa in the dissociated metallic phase. Molecules are found to be overstabilized using vdW, with a slightly shorter bond length, and with a stronger resistance to compression. As a consequence, pressure dissociation along isotherms using vdW is more progressive than computed with CEIMC. Below the critical point, the liquid-liquid phase transition is observed with both theories in the same density region but the one predicted by vdW has a smaller density discontinuity, i.e. a smaller first order character. The optical conductivity computed using Kubo-Greenwood is rather similar for the two systems and reflects the slightly more pronounced molecular character of vdW.

13 pages, 7 figures, submitted to Contribution to Plasma Physics

References in corpus (6)

• Advanced capabilities for materials modelling with Quantum ESPRESSO
• Nuclear Quantum Effects and Nonlocal Exchange-Correlation Functionals Applied to Liquid Hydrogen at High Pressure
• Stable liquid Hydrogen at high pressure by a novel ab-initio molecular dynamics
• Kubo-Greenwood Electrical Conductivity Formulation and Implementation for Projector Augmented Wave Datasets
• Phase diagram of hydrogen and a hydrogen-helium mixture at planetary conditions by Quantum Monte Carlo simulations
• Coupled Electron-Ion Monte Carlo simulation of hydrogen molecular crystals