Structure prediction of large cationic phosphorus clusters

Abstract

Guided by the mass spectrum of cationic phosphorus clusters produced in direct laser vaporization, we optimized nine P 8 isomers with density functional calculations and chose the most stable cuneane P 8 as building units for larger clusters. Eight isomers of P 25 + were proposed and full geometry optimizations were carried out with molecular mechanics, semi-empirical PM3 and density functional calculations. Then four models of P 33 + were built based on the most stable P 25 + and P 8 isomers. Other cationic phosphorus clusters up to P 89 + were also constructed. In these clusters, cuneane P 8 polymerizes to a long tubular shape with one extra phosphorus atom located at the end.