Theoretical Studies on the Potential Energy Surfaces of N8 Clusters

Abstract

The potential energy surfaces for the synthesis and decomposition reaction of N8(CS) → N5+ + N3- and isomerization reaction of N8(CS) to N8(C2h) were investigated by density functional theory (DFT). The species involved were fully optimized using four DFT methods. Relative energies were further calculated at the QCISD/6-311+G*//B3LYP/6-311+G* level. The barrier heights of N8(CS) → N5+ + N3- in forward and reverse directions were predicted to be 23.4 and 2.0 kcal/mol, respectively. Rate constants for the dissociation and synthesis pathways of N8(CS) were found by use of variational transition state theory. The barrier height for the isomerization reaction of N8(CS) to N8(C2h) was predicted to be 4.0 kcal/mol at the QCISD/6-311+G*//B3LYP/6-311+G* level.