The quintet population rise (red curve in Figure ) is clearly non-exponential, comprised of two apparent components, for ∼0-250 fs and ∼250-500 fs. Interestingly, we observe a very similar quintet population rise for the 0-250 fs region when excluding all 3 MC states, as for the unrestrained simulation, see Figure ; this seemingly assigns the 0-250 fs quintet component to the direct 3 MLCT → 5 MC transition (note that the quintet population here follows an exponential growth). However, we find that this direct 3 MLCT → 5 MC transition could only be operative in the absence of the 3 MC states. This is revealed by repeating the full simulation at varying 3 MLCT-5 MC spin-orbit coupling (SOC) strength: the quintet population dynamics are found to be insensitive of decreasing the 3 MLCT-5 MC SOC to zero, or increasing it by an order of magnitude, see the dotted lines in Figure . Importantly, this finding also shows that the sequential pathway via the 3 MC states dominates the mechanism, even in the case of enhanced 3 MLCT-5 MC coupling strength, due to e.g., nuclear distortions. Therefore, we here conclude that the direct 3 MLCT → 5 MC process has a negligible role in the photorelaxation.