Computational mechanistic study of methanol and molecular oxygen reaction on the triplet and singlet potential energy surfaces

摘要

The reaction of CH_3OH with the O_2 on the triplet and singlet potential energy surfaces (PES) was carried out using the B3LYP, MP2, and CCSD(T)//B3LYP theoretical approaches in connection with the 6-311++G(3df-3pd) basis set. Three pre-reactive complexes, ~1C1, ~1C2, and ~3C1, on the singlet and triplet PES were formed between methanol and molecular oxygen. From a variety of the complexes, seven types of products are obtained, of which four types are found to be thermodynamically stable. Results reveal that there exists one intersystem crossing between triplet and singlet PES. For P4 adduct that is the main and kinetically the most favorable product, the rate constants are calculated in the temperature range of 200-1,000 K in the reliable pathway.