Theoretical study of spin-orbit coupling and zero-field splitting in the spin-forbidden two-state reaction between cobaltacyclopentadiene and isocyanate

作     者：Lingling L Xiaofang Wang Yuancheng Zhu Xinwen Liu Kun Yuan Yongcheng Wang 

作者机构：College of Life Science and ChemistryTianshui Normal University College of Chemistry and Chemical EngineeringNorthwest Normal University 

出 版 物：《Chinese Science Bulletin》 (科学通报(英文版))

年 卷 期：2014年第59卷第3期

页      面：286-296页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(21263022) University Research Fund of Gansu Province Financial Department,and"QingLan"Talent Engineering Funds of Tianshui Normal University 

主　　题：轨道耦合 异氰酸酯 零场分裂 反应机理 自旋 B3LYP 三重态 交叉点 

摘      要：The two-state reaction mechanism of CpCo(C_4H_4)with isocyanate on the triplet and singlet potential energy surfaces has been investigated at the B3LYP level.A study is described for the computation of spin-orbit coupling of triplet state of the minimal energy crossing point(CP)with their singlet states and of the zerofield splitting(ZFS)parameters of the triplet states,including the full one-and two-electron terms of the BreitPauli *** are two key crossing points along this two-state reaction *** first crossing point—CP2 exists near^*** reacting system will change its spin multiplicity from the triplet state to the singlet state near this crossing *** the spin-orbit coupling interaction and ZFS D-tensor of the CP2 region are very strong,the reaction system will occur the reverse intersystem crossing from T_1 to S_***,its spin-flip efficiency may be *** second crossing point,CP3will again change its spin multiplicity from the singlet state to the triplet state in the Co-Cr bond activation pathway,leading to a decrease in the barrier height of^1TS(CF)from19.5 to 9.5 kcal/mol(1cal=4.182 J),and the efficiency of intersystem crossing from S_0 to T_1 is high because the larger spin-orbit coupling(SOC)matrix elements will result in the overpopulations of the three sublevels of T_1(3.30×10^(-1),3.32×10^(-1),and 3.38×10^(-1),respectively).