By contrast, the dynamics employing parameters of set B is very different. Despite mostly starting also in the higherlying singlet states S N , the adiabatic population bifurcates in an approximately 2:1 ratio. The smaller portion decays to the S 1 state -also initially populated by 15% -from where the whole singlet population relaxes to the adiabatic ground state S 0 (green curve), all within a ca. 100 fs time scale. The majority of the S N populations undergoes intersystem crossing to higher-lying triplet states T N (N≥ 2), which rapidly reach the T 1 state. From the T 1 state, the system undergoes back-intersystem crossing to the adiabatic ground-state S 0 , however, at a slower rate on a sub-1 ps time scale. This adiabatic S 0 state does not correspond to the diabatic S 0 state, i.e., the S 0 state at the Franck-Condon geometry, at least at early simulation times as discussed in more detail below.