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Manganese-containing active sites play essential roles in biological and chemical catalysis. Biologically, manganese enzymes are responsible for a wide variety of reactions, ranging from the breakdown of superoxide (by Mn superoxide dismutase) to photosynthetic water oxidation (by the Mn4Ca cluster in Photosystem II). In chemical catalysis, small molecule manganese complexes enable a range of oxidative transformations, including alkane hydroxylation and olefin epoxidation. In all these reactions, there is fundamental interest in understanding the transformations that occur at the manganese active site and hence an interest in directly probing the Mn electronic structure.