First principle structural determination of (B2O3)<i>n</i> (<i>n</i> = 1–6) clusters: From planar to cage

Abstract

The structure of (B2O3)n clusters (n = 1-6) are investigated using the method combining the genetic algorithm with density functional theory. Benchmark calculations indicate that TPSSh functional is reliable in predicting the energetic sequences of different isomers of (B2O3)n cluster compared to the high-level coupled cluster method. The global minimum (GM) structures of (B2O3)n clusters are planar up to n = 3, and cages at n = 4-6. A Td fullerene is found in the GM structure at n = 6. The stability of three-dimensional structures increases with the size of the cluster according to the analysis of the calculated atomization energy. Natural bonding analysis given by adaptive natural density partitioning reveals delocalized π-bonding in the 4-membered and 6-membered rings, and it is aromatic at the centers of cages and rings.