Statistically averaged molecular dynamics simulations of hydrogen diffusion in magnesium and magnesium hydrides

Abstract

Magnesium has a different crystal structure from its dihydride with hydrogenation leading to a phase transition from the hexagonal closely packed Mg into a tetragonal $\ensuremath{\alpha}\text{\ensuremath{-}}\mathrm{Mg}{\mathrm{H}}_{2}$ rutile type structure. Such materials exhibit complex hydrogen uptake and release kinetics because hydrogen diffusivities significantly change when the crystal structure changes. To provide a foundational understanding of (de)hydrogenation kinetics that is applicable to all stages of the reaction, we performed statistically averaged molecular dynamics simulations to derive hydrogen diffusivities as a function of temperature and hydrogen content for both magnesium and magnesium hydride. Our studies confirm that hydrogen diffusivities in magnesium hydride are much lower than in magnesium, in agreement with experimental data. Additionally, we observe that in either magnesium or magnesium hydride, higher hydrogen compositions result in reduced diffusivities. The latter was not revealed by prior experiments, which were conducted at fixed hydrogen composition. Finally, we discover a non-Arrhenius behavior in magnesium hydride. The physical origin of this behavior is also discussed.