Ludowieg Herbert D, Srebro-Hooper Monika, Crassous Jeanne, Autschbach Jochen
Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY-14260-3000, USA.
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387, Krakow, Poland.
ChemistryOpen. 2022 May;11(5):e202200020. doi: 10.1002/open.202200020.
The calculation of magnetic transition dipole moments and rotatory strengths was implemented at the zeroth-order regular approximation (ZORA) two-component relativistic time-dependent density functional theory (TDDFT) level. The circular dichroism of the spin-forbidden ligand-field transitions of tris(ethylenediamine)cobalt(III) computed in this way agrees very well with available measurements. Phosphorescence dissymmetry factors and the corresponding lifetimes are evaluated for three N-heterocyclic-carbene-based iridium complexes, two of which contain helicene moieties, and for two platinahelicenes. The agreement with experimental data is satisfactory. The calculations reproduce the signs and order of magnitude of , and the large variations of phosphorescence lifetimes among the systems. The electron spin contribution to the magnetic transition dipole moment is shown to be important in all of the computations.
在零阶正则近似（ZORA）双组分相对论含时密度泛函理论（TDDFT）水平上进行了磁跃迁偶极矩和旋光强度的计算。以这种方式计算的三（乙二胺）钴（III）自旋禁阻配体场跃迁的圆二色性与现有测量结果非常吻合。对三种基于N-杂环卡宾的铱配合物（其中两种含有螺旋烯部分）以及两种铂螺旋烯评估了磷光不对称因子和相应的寿命。与实验数据的吻合度令人满意。计算结果再现了磷光不对称因子的符号和量级，以及各体系中磷光寿命的巨大变化。在所有计算中，电子自旋对磁跃迁偶极矩的贡献都很重要。
