Coupled Electron-Ion Monte Carlo simulation of hydrogen molecular crystals

TL;DR

This study compares Coupled Electron-Ion Monte Carlo and DFT-based Path Integral Molecular Dynamics simulations to investigate the structural and electronic properties of high-pressure solid molecular hydrogen, revealing differences in stability and conductivity.

Contribution

It provides a direct comparison of CEIMC and PIMD methods for hydrogen crystals, assessing the accuracy of DFT xc approximations for quantum protons under extreme conditions.

Findings

PIMD shows larger atomic fluctuations than CEIMC.

C2c structure is stable up to 250 GPa in PIMD but up to 450 GPa in CEIMC.

Hydrogen becomes metallic around 350 GPa, reaching Drude-like behavior at 500 GPa.

Abstract

We performed simulations for solid molecular hydrogen at high pressures (250GPa$\leq$P$\leq$500GPa) along two isotherms at T=200 K (phases III and VI) and at T=414 K (phase IV). At T=200K we considered likely candidates for phase III, the C2c and Cmca12 structures, while at T=414K in phase IV we studied the Pc48 structure. We employed both Coupled Electron-Ion Monte Carlo (CEIMC) and Path Integral Molecular Dynamics (PIMD) based on Density Functional Theory (DFT) using the vdW-DF approximation. The comparison between the two methods allows us to address the question of the accuracy of the xc approximation of DFT for thermal and quantum protons without recurring to perturbation theories. In general, we find that atomic and molecular fluctuations in PIMD are larger than in CEIMC which suggests that the potential energy surface from vdW-DF is less structured than the one from Quantum Monte Carlo. We find qualitatively different behaviors for systems prepared in the C2c structure for increasing pressure. Within PIMD the C2c structure is dynamically partially stable for P$\leq$250GPa only: it retains the symmetry of the molecular centers but not the molecular orientation; at intermediate pressures it develops layered structures like Pbcn or Ibam and transforms to the metallic Cmca-4 structure at P$\geq$450GPa. Instead, within CEIMC, the C2c structure is found to be dynamically stable at least up to 450GPa; at increasing pressure the molecular bond length increases and the nuclear correlation decreases. For the other two structures the two methods are in qualitative agreement although quantitative differences remain. We discuss various structural properties and the electrical conductivity. We find these structures become conducting around 350GPa but the metallic Drude-like behavior is reached only at around 500GPa, consistent with recent experimental claims.