A density functional theory investigation of the polytopal rearrangement of square-based pyramidal clusters: C_5H_5~+, P_5~+ and Sb_5~+

摘要

The potential energy surface associated with the reaction of interconversion between two square-based pyramidal cations, C_5H_5~+, has been determined by density functional theory calculations. It confirms earlier studies that predicted a unique transition state of C_(2v) symmetry. The computed activation energy barrier (≈20 kcal/mol) indicates that the reaction is thermically feasible. Extension of this study to other isoelectronic systems (P_5~+ and Sb_5~+) shows that the process is easier with heavier elements.