Spin-orbit coupling and intersystem crossing in conjugated polymers: A configuration interaction description
Spin-orbit coupling and intersystem crossing in conjugated polymers: A configuration interaction description
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DOI：
10.1021/jp010187w
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发表时间：
2001-04-19
影响因子：
2.9
通讯作者：
Bredas, JL
中科院分区：
文献类型：
--
作者：
Beljonne, D;Shuai, Z;Bredas, JL
利用双光子相互作用理论计算了低聚噻吩和低聚亚苯基乙炔共轭链的单重态和三重态激发态。从单重态到三重态流形的系间交叉是通过自旋轨道耦合实现的，这导致了单重态（S-n）和三重态（T-n）波函数的混合。从一阶微扰理论得到的电子自旋轨道S-1-T-i矩阵元用于计算从最低单重激发态S-1到低三重态T-i的系间穿越速率。在此基础上，提出了描述共轭低聚物和共轭聚合物体系间交叉过程的一般机理。链长，重原子衍生化，和环扭曲的作用进行了评估。
Configuration-interaction calculations are performed to describe the singlet and triplet excited states of oligothiophene and oligo(phenylene ethynylene) conjugated chains. Intersystem crossing from the singlet to the triplet manifold is made possible by spin-orbit coupling, which leads to a mixing of the singlet (S-n) and triplet (T-n) wave functions. The electronic spin-orbit S-1-T-i matrix elements, obtained from first-order perturbation theory, are used to compute the rates of intersystem crossing from the lowest singlet excited state, S-1, into low-lying triplet states, T-i. On the basis of these results, a general mechanism is proposed to describe the intersystem crossing process in conjugated oligomers and polymers. The roles of chain length, heavy-atom derivatization, and ring twists are evaluated.