Quantum symmetrization transition in superconducting sulfur hydride from quantum Monte Carlo and path integral molecular dynamics

Abstract

We study the structural phase transition associated with the highest superconducting critical temperature measured in high-pressure sulfur hydride. A quantitative description of its pressure dependence has been elusive for any \emph{ab initio} theory attempted so far, raising questions on the actual mechanism driving the transition. Here, we reproduce the critical pressure of the hydrogen bond symmetrization in the Im$\bar{3}$m structure, in agreement with experimental data, by combining quantum Monte Carlo simulations for electrons with path integral molecular dynamics for quantum nuclei. For comparison, we also apply the self-consistent harmonic approximation, which underestimates the critical pressure by about 40 GPa even when the most accurate potential energy surface is used, pinpointing the importance of an exact treatment of nuclear quantum effects. They indeed play a major role in a significant reduction ($\approx$ 100 GPa) of the classical transition pressure and in a large isotope shift ($\approx$ 25 GPa) upon hydrogen-to-deuterium substitution