Optical Activity of Spin-Forbidden Electronic Transitions in Metal Complexes from Time-Dependent Density Functional Theory with Spin-Orbit Coupling |
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Authors: | Herbert D. Ludowieg Prof. Monika Srebro-Hooper Dr. Jeanne Crassous Prof. Jochen Autschbach |
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Affiliation: | 1. Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY-14260-3000 USA;2. Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krakow, Poland;3. Université Rennes, CNRS, ISCR – UMR 6226, 35000 Rennes, France |
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Abstract: | 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. |
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Keywords: | optical activity spin-forbidden transitions luminescence helicenes time-dependent density functional theory |
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