Computational Investigation on the Formation and Decomposition Reactions of the CHO Compound.

Gas-phase mechanism and kinetics of the formation and decomposition reactions of the CHO compound, a crucial intermediate of the atmospheric and combustion chemistry, were investigated using ab initio molecular orbital theory and the very expensive coupled-cluster CCSD(T)/CBS(T,Q,5)//B3LYP/6-311++G(3df,2p) method together with transition state theory and Rice-Ramsperger-Kassel-Macus kinetic predictions. The potential energy surface established shows that the CH + CO addition reaction has four main entrances in which CH + CO → (CHCCHCO) is the most energetically favorable channel. The calculated results revealed that the bimolecular rate constants are positively dependent on both temperatures ( = 300-2000 K) and pressures ( = 1-76,000 Torr). Of these values, the rate constant of the CH + CO → addition channel is dominant over the 300-2000 K temperature range, increasing from 1.53 × 10 to 1.04 × 10 cm molecule s with the branching ratio reducing from 62% to 44%. The predicted unimolecular rate coefficients in the ranges of = 300-2000 K and = 1-76,000 Torr revealed that the intermediate products , , and are rather unstable and would rapidly decompose back to the reactants (CH + CO), especially at high temperatures ( > 1000 K). The high-pressure limit rate constants for the CHO decomposition leading to products (CH + CO), (CHCCHCO + H), and (CHCO + CH) have been found to be in excellent agreement with the available literature values proposed by Tian et al. (, 756-773) without any adjustment from the ab initio calculations. Therefore, the predicted temperature- and pressure-dependent rate constants can be confidently used for modeling CO-related systems under atmospheric and combustion conditions.