Design of superatomic systems: exploiting favourable conditions for the delocalisation of d-electron density in transition metal doped clusters

Abstract

The incorporation of transition metals into superatomic species has led to the proposal of highly tailorable systems, with the transition metal atoms typically acting as magnetic dopants. However, the extent to which d-electrons are able to delocalise from their ionic cores has not been fully recognised. In this work a variety of systems have been explored using a range of exchange–correlation functionals commonly used to explore cluster species, to test the extent of d-electron delocalisation under favourable conditions. Early transition metals have been shown to readily delocalise their valence d-electrons for superatomic shell closing, with higher period atoms showing a greater tendency for delocalisation. Our findings also provide the framework for the design of superatomic systems with large numbers of electrons being contributed from a single atom.