Vargas, AlfredoZerara, MohamedKrausz, ElmarsHauser, AndreasLawson Daku, Latevi M2015-12-131549-9618http://hdl.handle.net/1885/85146State-of-the-art generalized gradient approximation (GGA) (PBE, OPBE, RPBE, OLYP, and HCTH), meta-GGA (VSXC and TPSS), and hybrid (B3LYP, B3LYP*, O3LYP, and PBE0) functionals are compared for the determination of the structure and the energetics of the D3 [Co(bpy)3]2+ complex in the 4A2 and 4E trigonal components of the high-spin 4T1g(t2g5 e g2) state and in the low-spin 2E state of octahedral 2Eg(t2g6 e g1) parentage. Their comparison extends also to the investigation of the Jahn-Teller instability of the 2E state through the characterization of the extrema of C2 symmetry of this spin state's potential energy surface. The results obtained for [Co(bpy) 3]2+ in either spin manifold are very consistent among the functionals used and are in good agreement with available experimental data. The functionals, however, perform very differently with respect to the spin-state energetics because the calculated values of the high-spin/low-spin energy difference ΔEHLel vary between -3212 and 3919 cm-1. Semilocal functionals tend to give too large ΔE HLel values and thus fail to correctly predict the high-spin state as the ground state of the isolated complex, while hybrid functionals tend to overestimate the stability of the high-spin state with respect to the low-spin state. Reliable results are, however, obtained with the OLYP, HCTH, B3LYP*, and O3LYP functionals which perform best for the description of the isolated complex. The optical properties of [Co(bpy) 3]2+ in the two spin states are also analyzed on the basis of electronic excitation calculations performed within time-dependent density functional response theory. The calculated absorption and circular dichroism spectra agree well with experimental results.200610.1021/ct60013842015-12-12