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Large database of high resolution Kb X-ray emission spectra of selected 3d metal (Ti, V, Cr, Mn) compounds obtained after excitation by 2 and 3 MeV proton beams have been built. Analysis of (relative) positions and intensities of Kb 00 and Kb 2,5 X-ray contributions as a function of chemical and structural properties of analyzed 3d metal compounds have been performed. Two independent experiments employing wavelength dispersive spectrometers with different experimental resolutions (8.1 eV versus 2.8 eV for the case of Cr Kb 1,3 line FWHM) were performed in order to exclude any possible effect of the experimental resolution on the extracted values. A simple parametrization of Kb 00 and Kb 2,5 X-rays' relative positions and intensities over the range of 3d metal compounds with various oxidation states, a wide range of metal-ligand bond lengths, and selected 3d metals, was performed. Results of our parametrization were compared critically with other experimental and theoretical values available in the literature. The parametrization obtained in this work could be used for chemical and structural speciation of 3d metal compounds and for improved interpretation of K X-ray spectra of 3d transition metal compounds measured by solid state detectors.

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Construction of a high energy resolution crystal X‐ray spectrometer to be used for wavelength‐dispersive X‐ray emission spectroscopy (WDXRS) may result in different geometrical aberrations, such as systematic X‐ray line shifts and changes of the X‐ray line shape. Most of these aberrations can be reduced by careful design of a crystal spectrometer, keeping the efficiency of the spectrometer as high as possible. The availability of high‐resolution position‐sensitive detectors and small excitation beam sizes, and therefore a possible downsized Wavelength‐dispersive X‐ray (WDX) spectrometer, increase the need for reliable simulation of aberrations involved in WDXRS. Since the experimental investigation of the impact that WDX spectrometer design has on a particular aberration is rather time‐consuming, a numerical X‐ray tracing procedure, XTRACE, has been developed and applied for this purpose. Results are given in the form of virtual X‐ray energy spectra that have been affected by the most important aberrations. Copyright © 2009 John Wiley & Sons, Ltd.