Structural properties and enthalpy of formation of magnesium hydride from quantum Monte Carlo calculations

M. Pozzo and D. Alfè
Phys. Rev. B 77, 104103 – Published 7 March 2008

Abstract

We have used diffusion Monte Carlo (DMC) calculations to study the structural properties of magnesium hydride (MgH2), including the pressure-volume equation of state, the cohesive energy, and the enthalpy of formation from magnesium bulk and hydrogen gas. The calculations employ pseudopotentials and B-spline basis sets to expand the single particle orbitals used to construct the trial wave functions. Extensive tests on system size, time step, and other sources of errors, performed on periodically repeated systems of up to 1050 atoms, show that all these errors together can be reduced to below 10meVf.u.. We find excellent agreement with the experiments for the equilibrium volume of both the Mg and the MgH2 crystals. The cohesive energy of the Mg crystal is found to be 1.51(1)eV and agrees perfectly with the experimental value of 1.51eV. The enthalpy of formation of MgH2 from Mg bulk and H2 gas is found to be 0.85±0.01eVf.u., or 82±1kJmole, which is off the experimental one of 76.1±1kJmole only by 6kJmole. This shows that DMC can almost achieve chemical accuracy (1kcalmole) on this system. Density functional theory errors are shown to be much larger and depend strongly on the functional employed.

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  • Received 8 November 2007

DOI:https://doi.org/10.1103/PhysRevB.77.104103

©2008 American Physical Society

Authors & Affiliations

M. Pozzo1 and D. Alfè1,2,3,*

  • 1Department of Earth Sciences and Materials Simulation Laboratory, University College London, Gower Street, London WC1E 6BT, United Kingdom
  • 2Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom
  • 3London Centre for Nanotechnology, University College London, 17-19 Gordon Street, London WC1H 0AH, United Kingdom

  • *d.alfe@ucl.ac.uk

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Vol. 77, Iss. 10 — 1 March 2008

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