Theoretical studies of the reactions of M+ (M = Ta, W, Re) with CS2

Abstract

Gas-phase CS2 activation by M+ (M = Ta, W, Re) was studied by the B3LYP density functional method.The geometries for reactants, transition states, and products were completely optimized. CS2 activation mediated by M+ (M = Ta, W, Re) were found to be a spin-forbidden process as a result of the crossing among the multistate energetic profiles. On the basis of the Hammond postulate, this was a typical two-state reactivity reaction. Among the different potential energy surfaces, the crossing points had been explored. The spin–orbit coupling (SOC) was also calculated between the electronic states of different multiplicities at the crossing point to estimate the intersystem crossing probability. For CP1, CP2, and CP4, the computed SOC constants were 80.28, 128.65, and 526.77 cm−1, which obtained by using one-electron spin–orbit Hamiltonian in Gaussian 09.