Based on the above, we thus identify a branching electronic relaxation mechanism with two components: i) MLCT → 3 MLCT → 3 MC → 1 GS with a short-lived MLCT component (∼200-300 fs), and ii) 1 MLCT → 3 MLCT with a long-lived 3 MLCT intermediate (∼10 ps or longer lived). The population dynamics up to 200 fs and thus the early appearance of 3 MC are supported by our simulation utilising the full (unconstrained) PESs and SOCs calculated on the fly, see Figure ; as is clear, the simulated LVC and full dynamics for 485 nm excitation show rather good agreement.