Ab Initio Study of Circular Dichroism and Circularly Polarized Luminescence of Spin-Allowed and Spin-Forbidden Transitions: From Organic Ketones to Lanthanide Complexes

Frédéric Gendron (1) , Barry Moore Ii (2) , Olivier Cador (1) , Fabrice Pointillart (1) , Jochen Autschbach (2) , Boris Le Guennic (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 SUNY Buffalo - University at Buffalo [SUNY]

Complete and restricted active space self-consistent field (CAS-/RAS-SCF) wave function methods are applied for the calculation of circular dichroism (CD) and circularly polarized luminescence (CPL) of a series of molecules comprising four organic ketones, the chiral cobalt(III) complex [Co(en)], and the europium(III) complex [Eu(DPA)]. The ab initio results are in good agreement with the experimental data and previous results obtained with Kohn-Sham density functional theory in the case of the spin-allowed transitions. CD and CPL properties are calculated ab initio for the spin-forbidden transitions of both a transition metal and a lanthanide complex.

Domains: Chemical Sciences; Theoretical and/or physical chemistry; Chemical Sciences; Coordination chemistry

Frédéric Gendron, Barry Moore Ii, Olivier Cador, Fabrice Pointillart, Jochen Autschbach, et al.. Ab Initio Study of Circular Dichroism and Circularly Polarized Luminescence of Spin-Allowed and Spin-Forbidden Transitions: From Organic Ketones to Lanthanide Complexes. Journal of Chemical Theory and Computation, 2019, 15 (7), pp.4140-4155. ⟨10.1021/acs.jctc.9b00286⟩. ⟨hal-02179645⟩