Theoretical Survey Of The Gas-Phase Reactions Of Allylamine With Co～+

Density functional theory (DFT) in its B3LYP functional has been used to survey the gas-phase reactions of allylamine with Co+. The potential energy surface (PES) and all the stationary points involved are analyzed in detail. The theoretical results are compared with the experimental findings that have been published earlier. More detailedly, geometries and bonding characteristics for all the stationary points involved are investigated at the B3LYP/6-311++G(d,p) level. Final energies are obtained by means of the B3LYP/6-311+G(2df,2pd) single-point calculations. In order to evaluate the general reliability of the levels of theory chosen, a comparison of experimentally known binding energies (BDE) with results from the B3LYP calculations is made for a set of representative relevant species. To gain a deep insight into the interaction between different functional groups, NBO analysis are carried out on several key minima at B3LYP/6-311++G(d,p) level. Values of are detected to evaluate if spin contamination can influence quality of the results for all the calculated species. For species with large spin contaminations, a stability test is made to check and correct the stability of wave function of these structures. Calculations on other spin state validates that there is no any crossing between the surfaces corresponding to different spins. The reaction of Co+ with allylamine is related to a single state and only the triplet surface (the ground surface) is thus considered. As for the reaction mechanisms, the NH3 elimination channel occurs through two different mechanisms, i. e., a directβ-H migration mechanism and a cylic-H migration mechanism. The former one starting with initial C-N bond activation is more favorable because all the minima and transition states involved are located below the entrance channel. NH2 elimination occurs accompanying the loss of NH3 and there are six possible channels for the elimination. The C2H2 elimination channels follow an initial C-C activation and two different ion products are formed arising from three different channels. We also calculate different mechanisms for the loss of H2 and eleven channels are located. The most favorable one is a 2,3-H2 elimination which involves an initial C-H activation.