Theoretical Study of the Reactivity of Mn~+ with CS_2

The reactions of Mn~+(~7S,~5S)with CS_2 have been studied at the B3LYP/TZVP level on both septuplet and quintet potential energy surfaces(PESs).The overall energies have been refined at the CCSD(T)level.The calculated results indicate that the reactions of Mn~+(~7S,~5S)with CS_2 proceed via an insertion-elimination mechanism.Calculations show that the quintet reaction is more favorable than the septuplet under high energy conditions.The spin-forbidden reaction Mn~+(7S)+ CS_2→MnS~+(~5Π) + CS proceeds through a septuplet-quintet surface and the crossing seam is approximately determined.All results have been compared with the existing experimental and theoretical data.