Exploring Ligand-to-Metal Charge-transfer States in the Photo-Ferrioxalate System using Excited-State Specific Optimization (2308.04932v1)

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