环丁酮光化学反应中S_1/T_1/S_0交叉点的重要作用  

Crucial Role of the S_1/T_1/S_0 Intersection Point in Photochemical Reaction of Cyclobutanone

作　　者：刘丹[1] 方维海[1] 傅孝愿[1] 

机构地区：[1]北京师范大学化学系,北京100875

出　　处：《物理化学学报》2000年第11期961-963,共3页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金!(29873008)

摘　　要：The role of the intersection between two potential energy surfaces has been more generally emphasizing on than before.In the present system,the intersections between S1,T1 and S0 surfaces were optimized with the state-averaged CAS(8,7)/6-31G method.The comparison of their optimized structures demonstrates that the intersection points of S1/S0 and S1/T1 locate in the same region,referred to as S1/T1/S0 point.The existence of S1/T1/S0 point and its high possibility of radiationless transition via intersystem crossing or internal conversion,would make the system have the most efficient funnel to generate the ground- and triplet-state products,which is consistent with the experimental facts.The role of the intersection between two potential energy surfaces has been more generally emphasizing on than before.In the present system,the intersections between S1,T1 and S0 surfaces were optimized with the state-averaged CAS(8,7)/6-31G method.The comparison of their optimized structures demonstrates that the intersection points of S1/S0 and S1/T1 locate in the same region,referred to as S1/T1/S0 point.The existence of S1/T1/S0 point and its high possibility of radiationless transition via intersystem crossing or internal conversion,would make the system have the most efficient funnel to generate the ground- and triplet-state products,which is consistent with the experimental facts.

关 键 词：环丁酮 S1/T1/S0交叉点 CASSCF 光化学反应 

分 类 号：O626.1[理学—有机化学] O644.1[理学—化学]