To begin, we summarize the insights gained in our simulations of the photodynamics of VCl 3 (ddpd). In Ref. 43, we used SH on LVC potentials that were parametrized at the CASSCF level of theory. As part of this work, we have repeated these simulations on potentials parametrized using a combination of CASSCF and CASPT2 calculations. In this combined CASSCF/CASPT2 approach, the CASSCF-based LVC potentials are modified using the more accurate CASPT2 vertical excitation energies. The mechanism of combined CASSCF/CASPT2 excited-state dynamics is qualitatively similar to the one based solely on CASSCF potentials and inspires the same hypothesis for improved photoluminescence properties. Thus, only the results from the combined CASSCF/CASPT2 calculations are presented in this manuscript. The computational details of these simulations as well as of all other calculations conducted in this work are reported in Section S1 in the SI. A more detailed discussion of the differences between the CASSCF and combined CASSCF/CASPT2 dynamics for VCl 3 (ddpd)can be found in Section S2 in the SI.