Long range coupling between defect centres in inorganic nanostructures: Valence alternation pairs in nanoscale silica

摘要

Valence alternation pair (VAP) states are formed by a closed-shell combination of two space- and charge-separated topological defect centres. These pairs of defects, although historically invoked to explain the electronic properties of bulk inorganic glassy materials (e.g., amorphous silicon dioxide) via the concept of negative-U defects, have more recently been found in a number of theoretical studies of silica surfaces and nanoscale silica clusters. Using density functional theory we systematically probe the structure and internal stability of VAPs in a number of silica nanoclusters with respect to the separation of the two constituent defect centres. We find that VAP states in nanosilica are strongly stabilised by the attractive electrostatic interaction between their separated oppositely charged component defects such that VAPs can persist up to an internal separation of a least 1.5 nanometres. Beyond this distance VAPs become unstable with respect to an open-shell combination of topological defects, virtually indistinguishable from two isolated open-shell defect centres. Finally, we theoretically analyse the possibility of experimental observation of VAP states through their infra-red vibrational spectra.