Each APC trial wave function is used to initialize a SA-CASSCF calculation, followed by MC-PDFT and NEVPT2 energy calculations. The states included in each SA-CASSCF calculation are chosen to remain consistent with the reference data. Generally, this means the inclusion of the ground state, the target excited state, and any lower states in the same irrep for the diatomic systems. For the two larger complexes, the calculation is state-averaged over all states of interest. Symmetry, as supported by PySCF, is imposed for all systems (described in detail in the supporting information) The best of the trial wave functions are then chosen with the aforementioned DVS procedure. When there are more than two states in the state-averaged wave function, DVS is applied by finding the state-averaged wave function which produces the lowest tPBE energy averaged over all states. Thus, for the two larger systems, DVS is used to select one set of state-averaged orbitals for all states of interest. For all systems, the converged wave functions are available in a repository hosted on Zenodo.