Quantum Monte Carlo Simulation of the High-Pressure Molecular-Atomic Crossover in Fluid Hydrogen

A first-order liquid-liquid phase transition in high-pressure hydrogen between molecular and atomic fluid phases has been predicted in computer simulations using ab initio molecular dynamics approaches. However, experiments indicate that molecular dissociation may occur through a continuous crossover rather than a first-order transition. Here we study the nature of molecular dissociation in fluid hydrogen using an alternative simulation technique in which electronic correlation is computed within quantum Monte Carlo methods, the so-called coupled electron-ion Monte Carlo method. We find no evidence for a first-order liquid-liquid phase transition.