Linear response separation of a solid into atomic constituents: Li, Al, and their evolution under pressure

Abstract

We present the first realization of the generalized pseudoatom concept introduced by Ball, and adopt the name enatom to minimize confusion. This enatom, which consists of a unique decomposition of the total charge density (or potential) of any solid into a sum of overlapping atomiclike contributions that move rigidly with the nuclei to first order, is calculated using (numerical) linear response methods, and is analyzed for both fcc Li and Al at pressures of 0, 35, and 50 GPa. These two simple fcc metals (Li is fcc and a good superconductor in the 20-40 GPa range) show different physical behaviors under pressure, which reflects the increasing covalency in Li and the lack of it in Al. The nonrigid (deformation) parts of the enatom charge and potential have opposite signs in Li and Al; they become larger under pressure only in Li. These results establish a method of construction of the enatom, whose potential can be used to obtain a real-space understanding of the vibrational properties and electron-phonon interaction in solids.