Metallic Bond - Localization and Clustering: From Bonding To Bonds

Localization and Clustering: From Bonding To Bonds

The metallic bonding in complicated compounds does not necessarily involve all constituent elements equally. It is quite possible to have an element or more that do not partake at all. One could picture the conduction electrons flowing around them like a river around an island or a big rock. It is possible to observe which elements do partake, e.g., by looking at the core levels in an X-ray photoelectron spectroscopy (XPS) spectrum. If an element partakes, its peaks tend to be skewed.

Some intermetallic materials e.g. do exhibit metal clusters, reminiscent of molecules and these compounds are more a topic of chemistry than of metallurgy. The formation of the clusters could be seen as a way to 'condense out' (localize) the electron deficient bonding into bonds of a more localized nature. Hydrogen is an extreme example of this form of condensation. At high pressures it is a metal. The core of the planet Jupiter could be said to be held together by a combination of metallic bonding and high pressure induced by gravity. At lower pressures however the bonding becomes entirely localized into a regular covalent bond. The localization is so complete that the (more familiar) H₂ gas results. A similar argument holds for an element like boron. Though it is electron deficient compared to carbon, it does not form a metal. Instead it has a number of complicated structures in which icosahedral B₁₂ clusters dominate. Charge density waves are a related phenomenon.

As these phenomena involve the movement of the atoms towards or away from each other, they can be interpreted as the coupling between the electronic and the vibrational states (i.e. the phonons) of the material. A different such electron-phonon interaction is thought to cause a very different result at low temperatures, that of superconductivity. Rather than blocking the mobility of the charge carriers by forming electron pairs in localized bonds, Cooper-pairs are formed that no longer experience any resistance to their mobility.