Fully consistent density functional theory determination of the insulator-metal transition boundary in warm dense hydrogen

Abstract

Using conceptually and procedurally consistent density functional theory (DFT) calculations with an advanced meta-generalized gradient approximation (GGA) exchange-correlation functional in ab initio Born-Oppenheimer molecular dynamics (BOMD) simulations, we determine the insulator-metal transition (IMT) of warm dense fluid hydrogen from 50 to 300 GPa to be in better agreement with experiment than previous DFT predictions. The inclusion of nuclear quantum effects via path-integral molecular dynamics (PIMD) sharpens the transition and lowers its temperature relative to the BOMD results. A rapid decrease in the molecular character of the system, as observed via the ionic pair correlation function, coincides with an abrupt conductivity increase, confirming a metallic transition due to molecular hydrogen dissociation that is coincident with abrupt band-gap closure. Comparison of the PIMD and BOMD results clearly demonstrates an isotope effect on the IMT. Exploitation of differing methodologies for using the orbital-dependent and deorbitalized versions of the meta-GGA enables us to quantify exchange-correlation approximation effects. Distinct from stochastic simulations, these results do not depend upon any clever but uncontrolled combination of ground-state and finite-T methodologies and should provide a reliable benchmark for further studies.