Computational Assessment of MLCT versus MC Stabilities in First-to-Third-Row d⁶ Pseudo-Octahedral Transition Metal...

An accurate modeling of metal-to-ligand-charge-transfer (MLCT) and metal-centered (MC) excited state energies is key to predict the photoinduced response in transition metal complexes (TMCs). Herein, the importance of the ground state and excited state reference geometries is addressed for three-prototype d⁶ pseudo-octahedral TMCs, each displaying a different potential energy landscape of MLCT versus MC relative stabilities. Several functionals are used within the time-dependent density functional theory (TDDFT), as well as multireference wave-function theory (MS-CASPT2), applied to [Mn(im)(CO)₃ (phen)]⁺ , [Ru(im)₂ (bpy)₂ ]²⁺ , and [Re(im)(CO)₃ (phen)]⁺ , (im: imidazole, bpy: bypiridine, phen: phenantroline). The results revel that TDDFT is robust except when using B3LYP functional for first-row d⁶ TMCs. In contrast, MS-CASPT2 calculations are strongly biased in those cases with competitive MLCT/MC states. The results reinforce the reliability of B3LYP to describe the excited states in d⁶ TMCs, but question the validity of assessing the density functional theory (DFT)/TDDFT performance via direct comparison with MS-CASPT2 performed at the same DFT reference geometry as a standard strategy. © 2019 Wiley Periodicals, Inc.