18-Electron Resonance Structures in the BCC Transition Metals and Their CsCl-type Derivatives.

Abstract

Bonding in elemental metals and simple alloys has long been thought of as involving intense delocalization, with little connection to the localized bonds of covalent systems. In this Article, we show that the bonding in body-centered cubic (bcc) structures of the group 6 transition metals can in fact be represented, via the concepts of the 18-n rule and isolobal bonding, in terms of two balanced resonance structures. We begin with a reversed approximation Molecular Orbital (raMO) analysis of elemental Mo in its bcc structure. The raMO analysis indicates that, despite the low electron count (six valence electrons per Mo atom), nine electron pairs can be associated with any given Mo atom, corresponding to a filled 18-electron configuration. Six of these electron pairs take part in isolobal bonds along the second-nearest neighbor contacts, with the remaining three (based on the t2g d orbitals) interacting almost exclusively with first-nearest neighbors. In this way, each primitive cubic network defined by the second-nearest neighbor contacts comprises an 18-n electron system with n = 6, which essentially describes the full electronic structure of the phase. Of course, either of the two interpenetrating primitive cubic frameworks of the bcc structure can act as a basis for this discussion, leading us to write two resonance structures with equal weights for bcc-Mo. The electronic structures of CsCl-type variants with the same electron count can then be interpreted in terms of changing the relative weights of these two resonance structures, as is qualitatively confirmed with raMO analysis. This combination of raMO analysis with the resonance concept offers an avenue to extend the 18-n rule into other transition metal-rich structures.