First-principles calculations of water dissociation on the oxygen-deficient (010) surface of Fergusonite-type LaNbO4 crystal

Abstract The water-containing atmosphere plays an important role in the improvement of proton conductivity of LaNbO 4 . The interaction between the water molecule and the oxygen-deficient (010) surface of LaNbO 4 crystal has been investigated via first-principles calculations. The water molecule is set at different heights over the oxygen vacancy and the exposed niobium atom in Nb–O tetrahedron. The adsorption and dissociation behavior of the water molecule to the surface are illustrated and analyzed by the total and localized density of states (DOS) plots. By finely adjusting the heights of the water molecule from the surface, the relatively stable position for the water molecule is determined by free energies of the hydrated slabs. The water molecule prefers to adsorb onto LaNbO 4 (010) surface and then to dissociate into one proton and one hydroxyl over the oxygen vacancy rather than over the exposed niobium atom in Nb–O tetrahedron.