We now assess how our simulated dynamics for [Fe(terpy) 2 ] 2+ obtained by the other DFT/TD-DFT methods compare with our previous B3LYP*-LVC results, which were found to agree with the most extensively analyzed time-resolved experimental data. We note that in contrast to the case of [Fe(bmip) 2 ] 2+ , for [Fe(terpy) 2 ] 2+ , quintet states cannot be neglected, as they clearly play an active role in the photorelaxation mechanism. Figure shows the excited-state dynamics of [Fe(terpy) 2 ] 2+ simulated by B3LYP* and the three GGA methods, RPBE, OPBE, and BLYP. As seen in Figure , all three GGA methods again yield rather similar population dynamics, but very different from the B3LYP* results: the 3 MLCT manifold is longer lived, the 5 MC population rise is slower, and the 3 MC intermediate states do not play any dominant role in the photorelaxation dynamics. These differences are well explained by the PESs shown in Figure : for GGAs, the minima of the 3 MLCT/ 3 MC/ 5 MC potentials are located at rather similar energies, while for B3LYP* there is a significant lowering in the direction of 3 MLCT → 3 MC → 5 MC (in line with the sequential mechanism). Importantly, this also has the consequence that the crossing of the 3 MLCT/ 3 MC and 3 MLCT/ 5 MC potentials are displaced from the 3 MLCT minimum geometry, which explains the slower dynamics of 3 MLCT and 5 MC states and the significantly decreased 3 MC population (in comparison to the B3LYP* case, see Figure ).