3-羟基丙烯醛单键旋转异构光反应机理的从头算研究

应用从头算分子轨道法分别在RHF/6-31G**和UHF/6-31G**水平上对3腔┤┓肿拥幕?S0)和三重激发态(T1)单键旋转异构反应机理进行了研究,优化出反应物和产物在S0态和T1态的4种平衡态和过渡态的几何构型,通过振动分析得到的虚频和计算的内禀反应坐标对过渡态进行了确认,并得到了零点能,根据基态和激发态反应途径分析了光反应机理。计算结果表明,基态和激发态的3腔┤┓肿拥ゼ旃狗从ξ焕萁系停嘏湃菀追⑸永砺凵涎橹ち斯夥从κ笛橹屑钢忠旃固宓拇嬖凇?

Ab Initio Researches on the Photoreaction Mechanism of the Single Bond Rotation of 3-Hydroxy acrolein

The photoreaction path of single bond rotation of 3-hydroxy acrolein has been studied by ab initio calculations at HF/6-31G** and UHF/6-31G** levels. Four stable reactants and four transition states of the ground state (S0) and excited state (T1) have been optimized. The zero point energy corrections were obtained by vibration analysis and the transition states were identified by the only virtue frequency. The intrinsic reaction coordinates (IRC) were also calculated. The rearrangement mechanism was analyzed according to the reaction path. The results show that the rearrangement barriers of 3-hydroxy acrolein are low no matter on the ground state (S0) or excited state (T1). The experimental structure is verified in theory.