X-ray spectroscopy of manganese clusters

Much of this thesis represents the groundwork necessary in order to probe Mn clusters more productively than with conventional Mn K-edge XAS and is presented in Part 1. Part 2 contains the application of x-ray techniques to Mn metalloproteins and includes a prognosis at the end of each chapter. Individual Mn oxidation states are more readily distinguishable in Mn L-edge spectra. An empirical mixed valence simulation routine for determining the average Mn oxidation state has been developed. The first Mn L-edge spectra of a metalloprotein were measured and interpreted. The energy of Mn K{beta} emission is strongly correlated with average Mn oxidation state. K{beta} results support oxidation states of Mn(III){sub 2}(IV){sub 2} for the S{sub 1} state of Photosystem II chemical chemically reduced preparations contain predominantly Mn(II). A strength and limitation of XAS is that it probes all of the species of a particular element in a sample. It would often be advantageous to selectively probe different forms of the same element. The first demonstration that chemical shifts in x-ray fluorescence energies can be used to obtain oxidation state-selective x-ray absorption spectra is presented. Spin-dependent spectra can also be used to obtain a more simplified picture of local structure. The first spin-polarized extended x-ray absorption fine structure using Mn K{beta} fluorescence detection is shown.