Where do the H atoms reside in PdHxsystems?

Abstract We present an ab initio density-functional theory study of PdH x systems. We evaluated the total energy of PdH x systems with the H atoms occupying interstitial (octahedral and tetrahedral) sites of a Pd supercell, allowing for the relaxation of the coordinates and supercell dimensions. The majority of our calculations were based on supercells consisting of four Pd atoms, and up to four H atoms, covering the range from x = 0.25 to x = 1. In addition some larger calculations are reported. In order to compare the relative stability of systems at different values of x (at fixed pressure and temperature T = P = 0), we computed the enthalpy of formation ΔH f (x) of the (non)stoichiometric systems. In the regime x = 0 → 1, the ΔH f (x) decrease in a manner indicative of the existence of attractive interactions between the dissolved H atoms. Ideal-solution theory cannot be applied to this system. Furthermore, we find that tetrahedral occupation is favoured over octahedral occupation at high x, leading to the formation of a zincblende structure at x = 1. A preliminary vibrational analysis of normal modes has been performed. Inclusion of vibrational zero-point energies in a harmonic approximation leads us to conclude, tentatively, that the observed stability of octahedral site occupation is due to more favourable zero-point energies of the H atoms in those sites. The results indicate that a proper understanding of this system must take into account the quantum nature of the dissolved hydrogen.