Ab initio quantum mechanical techniques, including the self-consistent-field (SCF), single and double excitation configuration interaction (CISD), single and double excitation coupled cluster (CCSD), and the single, double, and perturbative triple excitation coupled cluster [CCSD(T)] methods have been applied for the study of the HCCO(a4 A′) energy hypersurface. Rate constant measurements suggest an attractive potential for the reaction of CH(a 4Σ−) with CO. A vanishingly small energy barrier is predicted here in the CH(a 4Σ−) + CO reaction channel. We propose that a spin-forbidden electronic deactivation of CH(a 4Σ−) might occur through an intersystem crossing involving the a 4A″ state of HCCO. The energetics and the geometries of the reactants and products on both quartet and doublet energy surfaces are presented. The relationship between this research and experimental combustion chemistry is explored.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry