A theoretical investigation on fullerene-like phosphorus clusters

Representative fullerene-like phosphorus Pn clusters in the range of 14 ⩽ n ⩽ 60 are for the first time investigated with density functional theory (DFT) and Hartree–Fock (HF) methods. Total energies, structural properties, binding energies, and HOMO–LUMO gaps of several Pn clusters are systematically calculated and discussed. Present results indicate that all the Pn clusters found on local energy minima are unstable with respect to dissociation into P4 molecules, with their stability decreasing almost monotonically with the cluster size in the range of 14 ⩽ n ⩽ 40. In agreement with density functional tight-binding (DFTB) results, Pn clusters tend to behave differently from their Cn and Sin equivalents as evinced by their decreased stabilities, pentagon-fusion patterns, and more expanded structures.