Homoatomic d¹⁰–d¹⁰Interactions: Their Effects on Structure and Chemical and Physical Properties

Abstract

Abstract The distinction between valence electrons and essentially inactive core electrons is the basis of many classifying concepts in chemistry. However, it has recently been recognized that this is an oversimplification and should, at least in some areas of chemistry, be modified. Many cases are known where cations with closed d 10 configurations are subject to homoatomic interactions that influence structure and properties. A characteristic and surprisingly uniform structural feature (e.g., of a number of compounds containing monovalent coinage metals) is a clusterlike assembly of d 10 cations that corresponds in geometry and bond lengths to fragments of the metal structures themselves. Further evidence for a special type of bonding in such compounds is provided by their physical properties; for example, the absorption in the UV/VIS region shows a drastic redshift and the compounds are often conductors or semiconductors. The d electrons in such cases have obviously lost their pure “core” nature. All bonding models so far proposed for such systems involve mixing of higher orbitals.