Yu-Tzu Li Elise, Jiang Tzung-Ying, Chi Yun, Chou Pi-Tai
Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan.
Phys Chem Chem Phys. 2014 Dec 21;16(47):26184-92. doi: 10.1039/c4cp03540b. Epub 2014 Nov 3.
The main goal of this study is to provide systematic elucidation of the parameters that influence S → T intersystem crossing (ISC). Particular attention is paid to: (i) the computation of Sn→ Tm spin-orbit coupling strength based on a non-adiabatic approach, (ii) crucial factors that facilitate ISC, such as the atomic number, ligand structure, and particularly the types of electronic transition, (iii) formulating a discussion on the standpoints of the fundamental photophysical theory. Combining the theoretical and empirical approaches, we then make semi-quantitative assessment of the ISC rate for certain representative transition metal (TM) complexes, the results of which allow us to develop a set of empirical rules that harness ISC for organometallics analogous to El-Sayed's rule for the classic organic compounds. We therefore present a critical and timely theoretical approach with the results matching quantitatively the experimental data, which serves as a prototype to access the photophysics of TM complexes in a facile and precise manner beneficial to researchers in the field of optoelectronics.
本研究的主要目标是系统阐释影响S→T系间窜越（ISC）的参数。特别关注以下几点：（i）基于非绝热方法计算Sn→Tm自旋-轨道耦合强度；（ii）促进ISC的关键因素，如原子序数、配体结构，尤其是电子跃迁类型；（iii）从基本光物理理论的角度展开讨论。结合理论和经验方法，我们随后对某些代表性过渡金属（TM）配合物的ISC速率进行半定量评估，其结果使我们能够制定一套类似于经典有机化合物的埃尔-赛义德规则的利用ISC的有机金属经验规则。因此，我们提出了一种关键且及时的理论方法，其结果与实验数据定量匹配，为以简便且精确的方式研究TM配合物的光物理提供了一个范例，这对光电子学领域的研究人员有益。
