Iron site geometry in orthopyroxene: Multiple scattering calculations and XANES study

The iron site geometry in orthopyroxenes (OPX) and synthetic FeO, has been investigated by X-ray Absorption Near Edge Structure (XANES) spectroscopy. Multiple scattering calculations have been used to determine how the iron polyhedral geometry affects the absorption spectra. The results reported here demonstrate that this approach is effective in determining the site geometry around the absorbing atom, allowing the assignment of features in the XANES spectrum to specific structural aspects of the coordination environment. In the case of the orthopyroxenes this method allows discrimination between the multiple scattering contributions to the absorption spectrum due to the two octahedral sites M1 and M2 of the OPX structure. The results obtained with the MS calculation were used to evaluate the effects of polyhedral distortion, symmetry changes and iron site occupancies on the experimental spectra. The results indicate a more quantitative way to interpret XANES experimental spectra and give insights into the interpretation of site geometries of more complex or unknown structures and amorphous materials.