The influence of spin effects on the gas phase reactions of carbanions with N and O atoms.

Molecular anions have been recently detected in the denser regions of the interstellar medium. However, the chemical reactions of molecular anions with atomic species that are abundant in the ISM remain largely unexplored. This work is an experimental and computational study of CH(2)CN(-), CH(3)CHCN(-), (CH(3))(2)CCN(-), and CH(2)CHO(-) reacting with N and O atoms. In all cases the reactions of anions with O atoms exhibit larger reaction rate constants compared to the corresponding reactions with N atoms. Our study indicates that spin-forbidden reactions are the probable pathways in the reactions with N atoms, whereas spin-allowed reactions are the dominant processes in the reactions with O atoms. The major factor influencing the reaction rate constants of anions with N and O atoms is whether a spin-allowed barrierless pathway exists. The rich chemistry observed in this work provides a greater understanding of the ion-atom reaction processes, as well as some new avenues for further spin chemistry research.