Oxygen diffusion in hcp metals from first principles

Abstract

Oxygen interstitial site energies and migration barriers in 15 hexagonal close-packed (hcp) metals have been calculated with first-principles density functional theory. Multiple hcp systems show a preference for the hexahedral site over the tetrahedral site, as well as a stable crowdion site. More surprisingly, in more than half of the hcp systems, the oxygen does not choose the large octahedral interstitial as its ground state. We explain this result based on the effective valence of the metal from crystal-field splitting and the $c/a$ ratio. Diffusion constants for oxygen in all 15 hcp systems are calculated from analytically derived diffusion equations and match available experimental data.