The dominant roles of “electron-density-mechanism” and “chemical-bonding-mechanism” for hydrogen in molybdenum and lithium

• Mo is applicable for the optical diagnostics in nuclear fusion. • Li is designed to be first electrochemical monitoring system in fusion system. • Systematic DFT simulations for structural and thermodynamic properties of H in Mo/Li. • Vacancy act as a capturing center to cause H to accumulate in vacancy by an optimal electron-density-mechanism in Mo. • H atoms are unwilling to stay in vacancy but instead combine with adjacent Li atoms via a chemical-bonding-mechanism in Li. Using first-principles calculations, we have systematically studied structures and thermodynamic stability of interstitial H as well as the H-vacancy interaction in molybdenum (Mo) and lithium (Li). Single H atom prefers to occupy tetrahedral interstitial position (TIP) and octahedral interstitial position (OIP) in Mo and Li, respectively, and the solution energies are 0.87 eV and −0.66 eV, respectively. In Mo, mono-vacancy can capture as many as seven H atoms and each H atom prefers to bind onto an isosurface of valence electron density. However, H atoms detach from vacancy to occupy the OIPs outside vacancy in Li. Based on these results, we reveal that the electron-density-mechanism (EDM) and chemical-bonding-mechanism (CBM) cause different properties of H in Mo and Li, respectively. In Mo, since the valence electron density everywhere in interstitial lattice is much high, H atom has to search a place where the valence electron density must be suitable. Accordingly, vacancy can provide an optimal valence electron density region for H dissolution, and the optimal valence electron density is 0.10 electron/Å 3 at vacancy. In Li, H atom exhibits the negative solution energy in the interstitial lattice, which promotes H atom to form ionic bond with neighboring Li atom. H atoms do not combine inside vacancy but stay at the OIPs outside vacancy to form ionic bonds with neighboring Li atoms. We believe that the EDM and CBM can be generalized to other transition metals and other alkali metals, respectively.