of Table , we report the values of the partial photoisomerization quantum yields Φ ππ * upon ππ * excitation. The lower photoisomerization quantum yield after ππ * excitation has been previously discussed . It is related to an exception to Kasha's rule, resulting from a competition between "reactive" and "unreactive" internal conversion at the S 1 /S 0 conical intersection, i.e., between internal conversion with photoisomerization or without photoisomerization, respectively. Both processes require a certain degree of progress along the CNNC torsional coordinate. However, the unreactive S 1 →S 0 internal conversion process can occur earlier (i.e., farther from the 90 • midpoint of the torsional pathway) if more vibrational energy is available, as is typically the case with ππ * excitation. TSH-ODC, CTTSH-FGAC, and CTTSH-TGAC approaches presented photoisomerization quantum yields for ππ * in a very good agreement with the ones reported experimentally (0.09 -0.16), whereas TSH, CTTSH-FGLA, and CTTSH-TGLA were unable to do so. These last three FIG. . Populations of the S 0 state (in red) and of the S 1 state (in blue) as functions of time obtained from the calculations of the photodynamics of trans-azobenzene upon nπ * excitation using the four implementations of CTTSH. Thick lines refer to the fraction of trajectories F m (t) and thin lines refer to the average over the trajectories of the electronic populations P m (t). Reprinted with permission from Journal of Chemical Theory and Computation (2024) 20 (2), 580-596. Copyright 2024 American Chemical Society.