When referring to CASPT2 methods in 2010, Pierloot et al. noted "since full geometry optimizations at this correlated level are computationally far too expensive, we must settle for single-point calculations using structures obtained from DFT". They went on to study the electronic structure with DFT and WFT by varying one of the dihedral angles in the corrole, denoted Ω in Figure , using DFT-derived structures. The current study is inspired, in part, by this statement. In 2015, fully internally contracted (FIC)-CASPT2 analytical gradients, followed soon after by their multi-state extensions, 71 made such optimizations feasible. In the scan along the Ω angle using state-specific (SS)-CASPT2 and MS-CASPT2, Pierloot et al. find a state crossing for the bare and 5,10,15-triphenyl copper corroles, but see no such crossing in the MS-CASPT2 surface, attributing this to known failures in the multi-state approach. Here, we address the question of whether such differences between SS-CASPT2 and its multi-state analogues would emerge if the slice of the PES was based on CASPT2optimized structures. We also examine how DFT and CASPT2 optimized structures compare and explore other active space choices. Specifically, the molecular geometries and electronic structure of the unsubstituted and 5,10,15-triphenyl copper corroles were studied with DFT and WFT approaches. An electronic structure study is performed on the resulting molecular geometries followed by computing the PES along a linear interpolation between the S 0 and T 0 minima.