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).

Theoretical Study of the Kinetics of the Gas-Phase Reaction between Phenyl and Amino Radicals.

The potential energy surface (PES) of the CH + NH reaction has been investigated by using ab initio CCSD(T)//B3LYP/6-311++G(3df,2p) calculations. The conventional transition-state theory (TST) and the variable reaction coordinate-TST (VRC-TST) have been used to predict the rate constants for the channels possessing tight and barrierless transition states, respectively. The Rice-Ramsperger-Kassel-Marcus/Master equation (RRKM/ME) theory has been utilized to determine the pressure-dependent rate constants for these reactions.