The range-separated hybrid functional LC-BLYP deserves a separate discussion. Interestingly, while the population dynamics for [Fe(bmip) 2 ] 2+ simulated by LC-BLYP are very similar as for the other range-separated hybrid CAM-B3LYP and the two global hybrids B3LYP and PBE0, for [Fe(terpy) 2 ] 2+ , the population dynamics obtained by LC-BLYP are completely different from those obtained by the other three hybrid functionals. Furthermore, the 5 MC LVC potential for both complexes is placed energetically significantly higher (by ∼1.5 eV) compared to those calculated by the other three hybrids (see Figures and, for 3 MC states this energy difference is ca. three times smaller). Interestingly, this LC-BLYP calculated 5 MC energy curve for both complexes is very close to those calculated by the GGA methods; it is important to note that this only holds for 5 MC and not for all the other singlet and triplet excited states. These observations can be interpreted by noting that i) the quintet and singlet-triplet excited states in the current methodology are calculated differently, by unrestricted DFT (SCF) with imposing the spin multiplicity to be quintet and TD-DFT using the 1 GS reference (singlets-triplets), and ii) the part of the LC-BLYP exchange functional that is independent of the range separation in the original formulation is identical to the BLYP exchange functional, which is pure GGA, and exact exchange thus only appears in the variable part. Therefore, the obtained results for LC-BLYP can be explained by the variable (range-separation dependent) exact exchange acting only effectively in the TD-DFT formulation utilized for the computation of singlet-triplet excited states. Importantly, this leads to an inconsistency in the LC-BLYP calculated energies of the quintet and singlet-triplet excited states, which is reflected in the qualitatively wrong population dynam-ics of [Fe(terpy) 2 ] 2+ obtained by the LC-BLYP TSH simulation. It is however important to point out that the LC-BLYP functional was employed in its original form. In order to complete our assessment of exchange-correlation functionals, we use the optimally-tuned LC-BLYP method from ref. 61 (containing 20% exact exchange), for which the best agreement was obtained between TD-DFT and CASPT2 energies, to simulate the excited-stated dynamics of [Fe(bmip) 2 ] 2+ and [Fe(terpy) 2 ] 2+ ; the results are shown in Figure . For both complexes, the results are similar to those obtained by the hybrid functionals such as B3LYP; thus, for [Fe(bmip) 2 ] 2+ , the dynamics are dominated by the 3 MC component with no long-lived 3 MLCT state, whereas for [Fe(terpy) 2 ] 2+ , the fast 5 MC population rise via clear involvement of 3 MC states is observed. In fact. for [Fe(terpy) 2 ] 2+ , both the non-exponential nature of the 5 MC population curve and the 5 MC-3 MC oscillations are reproduced, albeit the latter are weaker than those identified in the dynamics simulated by B3LYP* (see Figure ). Therefore, the LC-BLYP results are drastically improved by optimal tuning, albeit the performance of B3LYP* is still superior (note, however, that that the tuning was not carried out for the studied Fe complexes but for a related [Fe(terpy) 2 ] 2+ derivative).