Chromium-Doped Germanium Clusters CrGe<i>_n</i> (<i>n</i> = 1−5): Geometry, Electronic Structure, and Topology of Chemical Bonding

Abstract

The structure and properties of small neutral and cationic CrGen(0,+) clusters, with n from 1 to 5, were investigated using quantum chemical calculations at the CASSCF/CASPT2 and DFT/B3LYP levels. Smaller clusters prefer planar geometries, whereas the lowest-lying electronic states of the neutral CrGe4, CrGe5, and cationic CrGe5+ forms exhibit nonplanar geometries. Most of the clusters considered prefer structures with high-spin ground state and large magnetic moments. Relative to the values obtained for the pure Gen clusters, fragmentation energies of doped CrGen clusters are smaller when n is 3 and 4 and larger when n = 5. The averaged binding energy tends to increase with the increasing number of Ge atoms. For n = 5, the binding energies for Ge5, CrGe5, and CrGe5+ are similar to each other, amounting to approximately 2.5 eV. The Cr atom acts as a general electron donor in neutral CrGen clusters. Electron localization function (ELF) analyses suggest that the chemical bonding in chromium-doped germanium clusters differs from that of their pure or Li-doped counterparts and allow the origin of the inherent high-spin ground state to be understood. The differential DeltaELF picture, obtained in separating both alpha and beta electron components, is consistent with that derived from spin density calculations. For CrGen, n = 2 and 3, a small amount of d-pi back-donation is anticipated within the framework of the proposed bonding model.