In the following, we address the ultrafast (sub-ps) quenching of 3 MLCT states by 3 MC, observed by fs-resolved XES. In fact, this is a remarkably striking result in light of the known photophysical behaviour of [Fe(bmip) 2 ] 2+ . This pathway was not considered in the TOAS assignment of Liu et al. in their original work reporting [Fe(bmip) 2 ] 2+ , and also challenges theoretical studies. For the theoretical modelling of this complex, first Fredin et al. calculated the potential energy surfaces (PESs) of using density functional theory (DFT) and timedependent DFT (TD-DFT). Subsequently, as mentioned in the Introduction, we performed quantum dynamics (QD) simulations using TD-DFT PESs along 4 and 5 chosen normal modes, which were all identified to possess dominant Fe-N/ Fe-C stretching character. We stress that this means a necessary drastic reduction in nuclear degrees of freedom, albeit the modes were carefully chosen based on calculated ab initio data and symmetry considerations. All these results supported the existence of a long-lived 3 MLCT state, without any sub-ps 3 MC component. Herein, we employ an alternative approach based on trajectory surface hopping (TSH). Importantly, in contrast to QD, which delivers solution to the time-dependent Schrödinger equation, TSH is not restricted by the number of nuclear degrees of freedom (DoF), as nuclear motion is described classically with electronic transitions approximated by stochastic hops. The dynamics thus occur on the full-dimensional PES and properties are calculated by averaging over numerous trajectories.