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The photo-ferrioxalate system (PFS), [Fe(III)(C$_2$O$_4$)]$^{3-}$, more thanan exact chemical actinometer, has been extensively applied in wastewater andenvironment treatment. Despite many experimental efforts to improve clarity,important aspects of the mechanism of ferrioxalate photolysis are still underdebate. In this paper, we employ the recently developed W$\Gamma$-CASSCF toinvestigate the ligand-to-metal charge-transfer states key to the ferrioxalatephotolysis. This investigation provides a qualitative picture of these statesand key potential energy surface features related to the photolysis. Ourtheoretical results are consistent with the prompt charge transfer picture seenin recent experiments and clarify some features that are not visible inexperiments. Two ligand-to-metal charge-transfer states contribute to thephotolysis of ferrioxalate, and the avoided crossing barrier between them islow compared to the initial photoexcitation energy. Our data also clarify thatone Fe-O bond cleaves first, followed by the C-C bond and the other Fe-O bond.

Exploring Ligand-to-Metal Charge-transfer States in the Photo-Ferrioxalate System using Excited-State Specific Optimization