Hydrogen dissociation on the Mg(0001) surface from quantum Monte Carlo calculations

Abstract

We have used diffusion Monte Carlo (DMC) simulations to calculate the energy barrier for H${}_2$ dissociation on the Mg(0001) surface. The calculations employ pseudopotentials and systematically improvable B-spline basis sets to expand the single particle orbitals used to construct the trial wavefunctions. Extensive tests on system size, time step, and other sources of errors, performed on periodically repeated systems of up to 550 atoms, show that all these errors together can be reduced to $\sim 0.03$ eV. The DMC dissociation barrier is calculated to be $1.18\pm 0.03$ eV, and is compared to those obtained with density functional theory using various exchange-correlation functionals, with values ranging between 0.44 and 1.07 eV.

6 pages, 4 figures, to appear in Physical Review B

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Cited by in corpus (8)

• Applications of quantum Monte Carlo methods in condensed systems
• Methods for calculating forces within quantum Monte Carlo simulations
• Averting the infrared catastrophe in the gold standard of quantum chemistry
• Plasmonic enhancement of molecular hydrogen dissociation on metallic magnesium nanoclusters
• Error Cancellation in Diffusion Monte Carlo Calculations of Surface Chemistry
• Ab initio statistical mechanics of surface adsorption and desorption: II. Nuclear quantum effects
• Influences of Al doping on the electronic structure of Mg(0001) and dissociation property of H2
• Quantum Monte Carlo prerequisites for industrial catalysts. Accurately assessing H atom and H${}_2$ physical adsorption energy on Pt(111)