VO2+与CH3CHO反应机理的密度泛函研究
Reaction Mechanisms between VO2+ and CH3CHO : A DFT Insight

用密度泛函方法在B3LYP/6-311G(d, p)水平上研究了VO2+氧化CH3CHO的反应机理。计算结果表明VO2+氧化CH3CHO的优势反应路径为：首先，CH3CHO与1VO2+ 或 3VO2+通过能垒的放热反应形成配合物；然后，VO2+的O原子进攻CH3CHO分子中-CHO的C原子，形成四元环中间体；最后，通过H迁移反应形成1VO+ 或 3VO+ 与CH3COOH的配合物。
The activation of acetaldehyde by VO2+ at gas phase has been theoretically investigated by using density functional theory (DFT) at B3LYP/ 6-311G (d, p) level. Calculation results indicate that the most favorable reaction routes between CH3CHO and VO2+ are as follows: firstly, complexes between 1VO2+ or 3VO2+ and CH3CHO are formed through barrier-free exothermic reaction, then four-membered cyclic intermediates are constructed by O atom of VO2+ attacking C atom of -CHO group in CH3CHO, and at last, complexes of 1VO+ or 3VO+ and CH3COOH are generated by H-migration reactions.