Methods for the quantification of statistically valid measures of the uncertainties associated with X-ray absorption fine structure (XAFS) data obtained from dilute solutions using fluorescence measurements are developed. Experimental data obtained from 10 mM solutions of the organometallic compound ferrocene, Fe(C(5)H(5))(2), are analysed within this framework and, following correction for various electronic and geometrical factors, give robust estimates of the standard errors of the individual measurements. The reliability of the refinement statistics of standard current XAFS structure approaches that do not include propagation of experimental uncertainties to assess subtle structural distortions is assessed in terms of refinements obtained for the staggered and eclipsed conformations of the C(5)H(5) rings of ferrocene. Standard approaches (XFIT, IFEFFIT) give refinement statistics that appear to show strong, but opposite, preferences for the different conformations. Incorporation of experimental uncertainties into an IFEFFIT-like analysis yield refinement statistics for the staggered and eclipsed forms of ferrocene which show a far more realistic preference for the eclipsed form which accurately reflects the reliability of the analysis. Moreover, the more strongly founded estimates of the refined parameter uncertainties allow more direct comparison with those obtained by other techniques. These XAFS-based estimates of the bond distances have accuracies comparable with those obtained using single-crystal diffraction techniques and are superior in terms of their use in comparisons of experimental and computed structures.
The x-ray mass-attenuation coefficient of copper was measured at 108 energies between 5 and 20 keV using synchrotron radiation. The measurements are accurate to between 0.09 and 4.5 %, with most measurements being accurate to better than 0.12%. The imaginary component of the form factor of copper was also determined after subtracting the attenuation contribution due to scattering. Measurements were made over an extended range of experimental parameter space, allowing us to correct for several systematic errors present in the data. These results represent the most extensive and accurate dataset of their type for copper in the literature and include the important and widely studied region of the K-edge and x-ray absorption fine structure. The results are compared with current theoretical tabulations as well as previous experimental measurements and expose inadequacies in both.
X-ray mass attenuation coefficients and imaginary components of the atomic form factor of zinc over the energy range of 7.2-15.2 keVThe x-ray mass attenuation coefficients of zinc are measured in a high-accuracy experiment between 7.2 and 15.2 keV with an absolute accuracy of 0.044% and 0.197%. This is the most accurate determination of any attenuation coefficient on a bending-magnet beamline and reduces the absolute uncertainty by a factor of 3 compared to earlier work by advances in integrated column density determination and the full-foil mapping technique described herein. We define a relative accuracy of 0.006%, which is not the same as either the precision or the absolute accuracy. Relative accuracy is the appropriate parameter for standard implementation of analysis of near-edge spectra. Values of the imaginary components f of the x-ray form factor of zinc are derived. Observed differences between the measured mass attenuation coefficients and various theoretical calculations reach a maximum of about 5% at the absorption edge and up to 2% further than 1 keV away from the edge. The measurements invite improvements in the theoretical calculations of mass attenuation coefficients of zinc.
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