Understanding Superatomic Ag Nanohydrides.

Bulk Ag hydrides are extremely challenging to make even at very high pressures, but they may become stable as the particle size shrinks to the nanometer regime. Here, the formation and electronic structure of Ag nanohydrides are investigated from a superatomic perspective by density functional theory. It is found that as the coverage increases, adsorption energy of hydrogen atoms on Ag38 cluster to form Ag38 H2 n nanohydride (n is from 1 to 15) can be energetically favorable with respect to bare Ag38 and H2 . Furthermore, the adsorbed hydrogen atoms contribute their 1s electrons to the superatom electron count and behave as a metal instead of a ligand. The electronic structure of the silver nanohydrides follows the superatomic complex model, leading to magic or relatively more stable compositions such as Ag38 H2 , Ag38 H20 , and Ag38 H30 , which correspond to 40-electron, 58-electron, and 68-electron shell closings, respectively. Angular momentum analyses of the superatomic orbitals suggest a convoluted interaction of geometry, symmetry, and orbital splitting.