A computational study on the insertion of n(2D) into a C—H or C—C Bond: The Reactions of N(2D) with Benzene and Toluene and Their Implications on the Chemistry of Titan

The reactions between nitrogen atoms in their first electronically excited state 2D with benzene and toluene have been characterized by electronic structure calculations of the stationary points along the minimum energy path. We focused our attention, in particular, to the channels leading to the imidogen radical for the first reaction implying the insertion of nitrogen into a C—H bond and to the NCH3 radical for the second reaction implying the insertion of nitrogen into a C—C bond. The minima along these reaction paths have been characterized using different ab initio methods in order to find a reasonable compromise between chemical accuracy and computational costs. Our results suggest that, while for geometry optimizations even relatively low level calculations are adequate, for energies higher level of calculations are necessary in order to obtain accurate quantitative results, in particular when strong correlation effects are present.