The level of quantum chemistry is a crucial factor for all excited-state dynamics simulations. For transition metal complexes, the state of the art of electronic structure theory is still heavily dominated by DFT/TD-DFT. While being computationally rather efficient, the PESs obtained by these methods may highly depend on the chosen exchange-correlation functional, in particular, when electronic states with different spin multiplicities are considered. Benchmarking DFT/TD-DFT results against higher-level calculations (e.g., CASPT2) and/or experimental data is thus valauble. However, such studies have been scarce for excited-state dynamics, which probe an extended region of PESs (in contrast to local equilibrium properties); this is especially true for transition metal complexes, with only one sole effort so far known, focusing on optimally tuning range-separated functionals for an Fe complex. Herein, we assess the performance of functionals belonging to different rungs of Jacob's ladder within the LVC framework and make extensive use of the existence of high-quality time-resolved experimental data obtained by X-ray emission spectroscopy, which is a sensitive probe for electronic states of transition metal complexes. 3.1 [Fe(bmip) 2 ] 2+