Investigating behavior of hydrogen in zirconium by first-principles: From dissolution, diffusion to the interaction with vacancy

By performing the first-principles calculations, we explore the dissolution and diffusion of hydrogen (H) in hexagonal closed packed zirconium (Zr) as well as its interaction with vacancy. We show that the tetrahedral (TE) interstitial site is the favorable trapping site for a single H atom with the solution energy of −0.45 eV. Such a negative solution energy is due to the strong electronic bond between H and neighboring Zr atoms. Moreover, the energy barrier for the migration of H from a TE site to its 1NN and 2NN TE site is 0.12 eV and 0.42 eV, respectively. It is noteworthy that the first path only slightly contributes to the experimentally measured H diffusivity in Zr, because the H atom is trapped by two nearest neighboring TE sites. Thus, the effective activation energy for H diffusion in Zr should be mainly determined by the second path, and the corresponding energy barrier is 0.42 eV. Furthermore, since the electronic density (available volume) in vacancy is lower (larger) than that of interstitial site, vacancy is a strong trap for H atoms in Zr. We demonstrate that the maximum of 8 H atoms can be accommodated in a mono-vacancy without the observation of H₂ molecule. These results can provide a basis to develop Zr materials in nuclear cladding devices.