Electronic structure and rebonding in the onion-like As@Ni12@As20 cluster

TL;DR

This paper provides an ab initio analysis of the geometry, electronic structure, bonding, and vibrational properties of the recently synthesized fullerene-like As@Ni12@As20 cluster, revealing its stability and bonding characteristics.

Contribution

It is the first computational study of the As@Ni12@As20 cluster, detailing its stability, electronic states, and bonding nature using ab initio methods.

Findings

The cluster is vibrationally stable.

Most stable in -3 oxidation state in condensed phase.

Most stable in -2 oxidation state in gas phase.

Abstract

We present the first ab initio study of the geometry, electronic structure, charged states, bonding and vibrational modes of the recently synthesized fullerene-like As@Ni12@As20 cluster which has icosahedral point symmetry [Science, 300, 778 (2003)]. We show that the molecule is vibrationally stable and will be electronically most stable in its -3 oxidation state in the condensed phase and in -2 state in the gas phase. We examine the bonding in this unusually structured molecule from charge transfer between atoms, infrared and Raman spectra, and charge density isosurfaces.