Soft X-ray spectroscopy of ferrous silicates

Energy gaps and electrical conductivities in the ferrous silicates, Fe₂SiO₄ and FeSiO₃, depend primarily on Fe-O bonding and may be studied by ultraviolet and soft X-ray spectroscopy. We have measured FeL_II–III X-ray band spectra under conditions of “minimal” (I₄, at 4.0 keV) and “high” (I₁₀, at 10.0 keV) self absorption to determine 3d orbital energy levels, to delineate d states in the valence band, and to construct band gap models. Absorption spectra, I₄/I₁₀, were computed to determine vacant orbital levels in the gap. A difference function (I₄–I₁₀) has been proposed to identify X-radiation at photon energies above the measured L_III absorption edge, including high-energy, double-vacancy satellites and radiative transitions involving the anti-parallel (spin-down) d ⁶ electron in the ground state. The proposed band gap model for Fe₂SiO₄ is consistent with that of Nitsan and Shankland (1976), including an intrinsic transition of 6.5 eV and an energy gap of 7.8 eV. The 3d orbital energy level electronic structures are in general agreement with levels computed by Tossell et al. (1974) for [FeO₆]^10? in FeO using an SCF Xα cluster MO method. A high-energy, double-vacancy satellite was found at ～710.7 eV, and is presumed to originate from an L_IIIM_II,III initial state. The intensity of these satellites for the ferrous silicates and other iron compounds, and corresponding Fe L_II/L_III intensity ratios are correlated with differences in band gap magnitudes and gap structure. Fe L_II/L_III intensity ratios are not well correlated with iron oxidation state.