Optical Activity of Spin-Forbidden Electronic Transitions in Metal Complexes from Time-Dependent Density Functional Theory with Spin-Orbit Coupling.

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 g lum 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 g lum , 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.