3A＇ and 3A＂ Energy Surfaces for the VS＋ ＋ CO2→VO＋ ＋ COS Reaction

摘要

cqvip:The title reaction proceeds via a one- and two-step mechanism along the 3A" and 3A’ surfaces, respectively. The 3A’ excited state surface has a lower barrier than the 3A" ground state surface (11.6 and 16.0 kcal/mol, respectively). We suggest that, at low energies, the reaction proceeds along the A’ surface and then makes an intersystem crossing to the A" surface and yields the ground state product VO+(3∑-), which may explain the small VO+ cross-section at low energies observed in the