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Abstract

The search for technologically and economically viable storage solutions for hydrogen fuel would benefit greatly from research strategies that involve systematic property tuning of potential storage materials via atomiclevel modification. Here, we use first-principles density-functional theory to investigate theoretically the structural and electronic properties of ultrathin Mg films and Mg-based alloy films and their interaction with atomic hydrogen. Additional delocalized charges are distributed over the Mg films upon alloying them with 11.1% of Al or Na atoms. These extra charges contribute to enhance the hydrogen binding strength to the films.We calculated the chemical potential of hydrogen in Mg films for different dopant species and film thickness, and we included the vibrational degrees of freedom. By comparing the chemical potential with that of free hydrogen gas at finite temperature (T) and pressure (P), we construct a hydrogenation phase diagram and identify the conditions for hydrogen absorption or desorption. The formation enthalpies of metal hydrides are greatly increased in thin films, and in stark contrast to its bulk phase, the hydride state can only be stabilized at high P and T (where the chemical potential of free H2 is very high). Metal doping increases the thermodynamic stabilities of the hydride films and thus significantly helps to reduce the required pressure condition for hydrogen absorption from H2 gas. In particular, with Na alloying, hydrogen can be absorbed and/or desorbed at experimentally accessible T and P conditions