Su Ming-Der
Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan.
J Phys Chem A. 2008 Jan 17;112(2):194-8. doi: 10.1021/jp710522n. Epub 2007 Dec 21.
The mechanisms of photoisomerization reactions were investigated theoretically using a model system of 2-methylfuran with the CASSCF (10-electron/8-orbital active space) and MP2-CAS methods and the 6-311(d,p) basis set. After 2-methylfuran molecules are produced in the T(1) state by photoexcitation at 254 nm, intersystem crossing to the S(0) surface is the most probable pathway for deactivation. Relaxing to the S(0) state, the 2-methylfuran molecules can dissociate into 3-methylcyclopropene and carbon monoxide products. Otherwise, they may revert to singlet 2-methylfuran or undergo photorearrangement to produce 3-methylfuran. These stepwise mechanisms are consistent with the available experimental observations.
使用具有CASSCF（10电子/8轨道活性空间）和MP2-CAS方法以及6-311(d,p)基组的2-甲基呋喃模型系统，从理论上研究了光异构化反应的机制。在254 nm光激发下，2-甲基呋喃分子以T(1)态产生后，系间窜越至S(0)表面是最可能的失活途径。弛豫至S(0)态时，2-甲基呋喃分子可分解为3-甲基环丙烯和一氧化碳产物。否则，它们可能恢复为单重态2-甲基呋喃或发生光重排生成3-甲基呋喃。这些逐步机制与现有的实验观察结果一致。
