The electronic structure description of the PES has a decisive impact on the simulated dynamics. For transition metal complexes, in particular in case of excited states, quantum chemistry faces immense challenges such as the description of electronic degeneracies, high density of states, and charge transfer excited states. Ideally, a balanced multiconfigurational treatment such as multiconfigurational second-order perturbation theory (CASPT2) would be the method of choice, however, computational feasibility issues as well as variance of the utilised active space for the nuclear configurational space explored by the dynamics severely limits its applicability. Herein, we use our efficient DFT/ TD-DFT framework based on the B3LYP* exchange-correlation functional , which we benchmarked extensively against experimental 22,23 and CASPT2 data . We carry out the TSH dynamics both on DFT/TD-DFT PESs, according to a linear vibronic coupling (LVC) harmonic model (which allows simulations up to several ps), and full on-the-fly ab initio PESs (in order to assess the validity of the LVC model for short sub-ps timescales). Details of the utilised methodology are described in the Methods section and the Electronic Supplementary Information (ESI).