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Free energy methods in coupled electron ion Monte Carlo

Recent progress in simulation methodologies and in computer power allow first-principles simulations of condensed systems with Born–Oppenheimer electronic energies obtained by quantum Monte Carlo methods. Computing free energies and therefore getting a quantitative determination of phase diagrams is one step more demanding in terms of computer resources. In this paper we derive a general relation to compute the free energy of an ab initio model with Reptation Quantum Monte Carlo (RQMC) energies from the knowledge of the free energy of the same ab initio model in which the electronic energies are computed by the less demanding but less accurate Variational Monte Carlo (VMC) method. Moreover we devise a procedure to correct transition lines based on the use of the new relation. In order to illustrate the procedure, we consider the liquid–liquid phase transition in hydrogen, a first-order transition between a lower pressure, molecular and insulating phase and a higher pressure, partially dissociated and conducting phase. We provide new results along the T = 600 K isotherm across the phase transition and find good agreement between the transition pressure and specific volumes at coexistence for the model with RQMC accuracy between the prediction of our procedure and the values that can be directly inferred from the observed plateau in the pressure–volume curve along the isotherm. This work paves the way for future use of VMC in first-principles simulations of high-pressure hydrogen, an essential simplification when considering larger system sizes or quantum proton effects by Path Integral Monte Carlo methods.

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