Novel ground state structures of N-doped LuH3

Ab-initio crystal structure searches have played a pivotal role in recent discoveries of high-Tc hydride superconductors under high pressure. Using evolutionary crystal searches, we predict novel ground state structures of N-doped LuH 3 at ambient conditions. We find an insulating ground state structure for LuN 0.125 H 2.875 (∼1.0 wt.% N), contrary to earlier studies where assumed structures were all metallic. This insulating behavior of ground state was found to persist up to ∼45 GPa. However our crystal structure searches revealed a metallic state for an H-deficient variant of LuN 0.125 H 2.875 . We study bonding characteristics of important structures by calculating electronic density of states, electronic-localization functions and Bader charges. Our Bader charge analysis shows that insulators have both H + and H − ions whereas metals have only H − ions. We find that H + ions are bonded to N atoms via a very short covalent bond. Thus we identify a clear relationship between formation of N–H bonds and insulating behavior of materials. Besides this, we perform crystal structure searches for three more compositions with higher N-content (>1.0 wt.%). Analysis of electronic properties shows that the ground states of these compositions are insulator.