苯甲醛低温氧化主导反应速率系数从头算:C₆H₅ĊO+O₂加成反应

Benzoyl radical(C₆H₅ĊO)is a primary intermediate of benzaldehyde oxidation, which is mainly decomposed in the previous studies without considering the oxygen addition reaction. In order to clarify the importance of acyl radical addition to oxygen in aldehydes oxidation particularly at low temperatures, the effect of acetyl addition to oxygen in acetaldehyde oxidation at low temperatures is examined at first. Then, the potential energy surface of C₆H₅ĊO+O₂ is evaluated at the level of DLPNO-CCSD(T)/cc-pVTZ//M06-2X/6-311++G(d, p). Based on the RRKM/ME method, the micro-canonical variational transition state theory(VTST) is used to obtain the temperature and pressure dependent reaction rate coefficients, providing important reference for the improvement of benzaldehyde oxidation mechanism at low temperatures. In addition, the effect of newly calculated reac-tion channels on the oxidation mechanism of benzaldehyde is investigated, and it is revealed that the effects of newly calculated reactions on benzaldehyde sub-mechanisms differ significantly. The main cause is the difference in the thermodynamic parameters of key species involved in the benzaldehyde oxidation reactions of different models.