Atomic Radii and Interatomic Distances in Metals

Abstract

The problem of the nature of the interatomic farces in the elementary metals and in intermetallic compounds and other alloys continues to be puzzling, despite the clarification of some questions which has been provided by quantum mechanical considerations. It has been my opinion, contrary to that of other investigator that the metallic bond is very closely related to the covalent (shared-electron-pair) bond, and that each atom in a metal may be considered as forming covalent bonds with neighboring atoms, the covalent bonds resonating among the available interatomic positions. It was shown in the first paper of this series that the number of covalent bonds resonating among the available positions about an atom (the metallic valence of the atom) increases from one to nearly six (5.78) in the sequence K, Ca, Sc, Ti, V, Cr in the first long period of the periodic table, remains nearly constant from Cr to Ni, and begins to decrease with Cu. This concept, which is substantiated by the magnetic properties of the metals and their alloys, provides a qualitative explanation of many properties of the transition metals (including those of the palladium and platinum groups), such as characteristic temperature (heat capacity at low temperatures), hardness, compressibility, coefficient of thermal expansion, and the general trend of interatomic distances. It will be shown in the following pages that it also permits the formulation of a system of atomic radii which can be used for the calculation of interatomic distances in metals and intermetallic compounds and for the interpretation of observed interatomic distances in terms of the electronic structure of the crystals. These atomic radii (which may be called metallic radii) are found, as expected, to show an intimate relation to the covalent radii of the atoms-a relation which, in its general nature, permitted Goldschmidt over twenty years ago to use data taken from both metals and ordinary covalent crystals in formulating a table of atomic radii, and which has been recognized3 as providing very strong support for the concept that metallic bonds are essentially resonating covalent bonds.