Quantum Monte Carlo Study of High Pressure Solid Molecular Hydrogen

TL;DR

This study employs advanced quantum Monte Carlo methods to map the phase diagram of solid molecular hydrogen under high pressure, identifying structural transitions and metallization pressures with high accuracy.

Contribution

It introduces a new finite-size correction method combining twist-averaged boundary conditions with KZK functional corrections for improved phase diagram calculations.

Findings

Insulating Cmca-12 structure transitions to metallic at around 375 GPa.

Zero-point energy effects extend the stability of Cmca-12 up to 430 GPa.

The P6_3/m structure remains stable up to 220 GPa, consistent with experimental data.

Abstract

We use the diffusion quantum Monte Carlo (DMC) method to calculate the ground state phase diagram of solid molecular hydrogen and examine the stability of the most important insulating phases relative to metallic crystalline molecular hydrogen. We develop a new method to account for finite-size errors by combining the use of twist-averaged boundary conditions with corrections obtained using the Kwee-Zhang-Krakauer (KZK) functional in density functional theory. To study band-gap closure and find the metallization pressure, we perform accurate quasi-particle many-body calculations using the $GW$ method. In the static approximation, our DMC simulations indicate a transition from the insulating Cmca-12 structure to the metallic Cmca structure at around 375 GPa. The $GW$ band gap of Cmca-12 closes at roughly the same pressure. In the dynamic DMC phase diagram, which includes the effects of zero-point energy, the Cmca-12 structure remains stable up to 430 GPa, well above the pressure at which the $GW$ band gap closes. Our results predict that the semimetallic state observed experimentally at around 360 GPa [Phys. Rev. Lett. {\bf 108}, 146402 (2012)] may correspond to the Cmca-12 structure near the pressure at which the band gap closes. The dynamic DMC phase diagram indicates that the hexagonal close packed $P6_3/m$ structure, which has the largest band gap of the insulating structures considered, is stable up to 220 GPa. This is consistent with recent X-ray data taken at pressures up to 183 GPa [Phys. Rev. B {\bf 82}, 060101(R) (2010)], which also reported a hexagonal close packed arrangement of hydrogen molecules.