Nonlocal Electronic Correlations in the Cohesive Properties of High-Pressure Hydrogen Solids.

Abstract

High-pressure hydrogen exhibits remarkable phenomena including the insulator-to-metal (IM) transition; however, a complete resolution of its phase diagram is still an elusive goal despite many efforts and much controversy. Theoretical modeling is typically based on density functional theory (DFT) with a mean-field description of electronic correlations, which is known to be rather limited in describing IM transitions. Herein, we show that nonlocal electron correlations play a central role in the relative stability of solid hydrogen phases, and that DFT-correcting for these correlations by the many-body dispersion (MBD) model reaches the accuracy of quantum Monte Carlo (QMC) simulations and predicts the same C2/c-24 → Cmca-12 → Cs(IV) IM transition. In contrast with the conventional assumption that many-body electronic correlations become localized in metallic systems because of exponential screening with interelectronic distance, we find that the anisotropy of the electronic response of hydrogen solids under pressure leads to longer-ranged many-body effects in metallic phases relative to insulating ones. This refines our understanding of phase diagram of hydrogen solids as well as anisotropic many-body correlations.