Cu and Ag as one-valence-electron atoms: Pseudopotential results for Cu2, Ag2, CuH, AgH, and the corresponding cations

Abstract

Semiempirical pseudopotentials, representing singly ionized X⁺ cores, have been adjusted for the Cu and Ag atoms. Polarization of the X⁺ cores (including core‐valence correlation) is explicitly taken into account. Deviations of (unpolarized) core interactions, X⁺–X⁺ and X⁺–H⁺, from point‐charge behavior are treated at the SCF level. Valence correlation is included within the framework of the spin‐density functional formalism. Results are given (i) for atomic dipole polarizabilities and electron affinities, (ii) for bond lengths and dissociation and ionization energies of the diatomics XH^m+ and X^m+₂ (X=Cu, Ag; m=0, 1). The accuracy of our results for the dimers is 0.1 eV for binding energies and 0.05 Å for bond lengths. In contrast to the situation for the alkali dimers, Cu⁺₂ and Ag⁺₂ prove to be less strongly bound than the corresponding neutral dimers.