气态烯丙醇光异构化反应的理论研究

本文采用自洽场分子轨道UHF/6-31G从头计算法, 辅以能量梯度法研究气相烯丙醇光异构化反应的机理。全部优化了T1态势能面上反应物、过渡态、中间体和产物的几何构型。基于Fukui提出的内禀反应坐标理论(IRC)计算这一体系的反应途径, 并针对各驻点进行MP2/6-31G的相关能校正, 得到该反应在激发态进行并为一经历双自由基中间体的分步反应的结论。支持了实验工作者提出的机理。

Quantum chemical investigation of the photo-rearrangement of allyl alcohol

The geometries of the reactant, the intermediate, the transition state and the product in T1 state for the photo-rearrangement of allyl alcohol to propionaldehyde are optimized by gradient technique, based on UHF ab initio methods with 6-31G basis set. The whole reaction path (intrinsic reaction coordinate proposed by Fukui) is traced. Our results of calculation with correlation correction by means of MP2/6-31G method not only support that the photorearrangement of allyl alcohol proceeds via hydrogen shift in the excited electronic state, but also predict that the isomerization is a two step reaction via a diradical as an intermediate with the main primary product excited propenol.