Su Ming-Der
Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan.
J Phys Chem A. 2007 Feb 8;111(5):971-5. doi: 10.1021/jp064928a.
The potential energy surfaces corresponding to the photochemical reactions of pyridine, phosphinine, and arsabenzene have been investigated by employing the CAS(6,6)/6-311G(d,p) and MP2-CAS-(6,6)/6-311++G(3df,3pd)//CAS(6,6)/6-311G(d,p) methods. The thermal (or dark) reactions of these reactant species have also been examined using the same level of theory. The mechanisms of drastic structural change in the excited- and ground-state reactions of pyridine, phosphinine, and arsabenzene and the differences between them are elucidated. The theoretical investigations suggest that conical intersections play a crucial role in their photoisomerization reactions. The results obtained allow a number of predictions to be made.
通过采用CAS(6,6)/6-311G(d,p)和MP2-CAS-(6,6)/6-311++G(3df,3pd)//CAS(6,6)/6-311G(d,p)方法，研究了吡啶、磷苯和砷苯光化学反应的势能面。还使用相同的理论水平研究了这些反应物物种的热（或暗）反应。阐明了吡啶、磷苯和砷苯在激发态和基态反应中剧烈结构变化的机制以及它们之间的差异。理论研究表明，锥形交叉点在它们的光异构化反应中起着关键作用。所得结果使得能够做出许多预测。
