The chemical bond in solids—revisited

Abstract

Abstract This article complements an earlier topical review of the chemical bond (Jones 2018 J. Phys.: Condens. Matter 30 153001), starting in the mid-19th century and seen from the perspective of a condensed matter physicist. The discussion of applications focused on the structure and properties of phase change materials. We review here additional aspects of chemistry, particularly some that have raised interest recently in this context. Concepts such as ‘electron-rich’, ‘electron-deficient (excess orbital)’, ‘hypervalent’, ‘three-centre’, and ‘metavalent’ bonds, and ‘multicentre hyperbonding’ are now found in the condensed matter literature. They are surveyed here, as well as the bond in metals and the ‘Peierls’ distortion. What are these concepts, are they related, and are they sometimes new labels for established, but unfamiliar ideas? ‘Half bonds’ and ‘fractional valencies’ play a central role in this discussion. It is remarkable that they were introduced 100 years ago, but ignored or forgotten, and have needed to be rediscovered more than once.