Upon analyzing the geometrical changes throughout the dynamics, we observed a considerable increase in the flexibility in the excited state, particularly around the pyrone ring. Consequently, the value of the standard deviation of the energy gap distribution more than doubles, going from 0.119 eV for VEEs to 0.285 eV for VDEs, see Table . However, once the geometries are optimized in frozen QM solvent, the standard deviation values decrease to 0.077 and 0.097, respectively.