Figure 4.

Simulated population dynamics upon ¹T_1g photoexcitation. The four panels show the results for different approaches: (a) full-dimensional TSH on LVC-B3LYP* potentials and 3D-QD on (b) VCHAM-B3LYP*, (c) LVC-B3LYP*, and (d) VCHAM-CASPT2 PESs. Note that the TSH and QD populations are made consistent by summing up the excited-state populations for the same spin multiplicity (singlet, triplet, quintet). The dashed lines represent exponential fits with the functions exp(−t/τ) and 1 – exp(−t/τ) for ¹T_1g and ⁵T_2g, respectively.