Parameter refinement in the analysis of X-ray irradiated samples

Although the refinement of parameters is a well known method in the scope of X-ray diffraction, it also appears as a powerful tool in other spectroscopic techniques. This work presents a method for the refinement of different atomic and experimental parameters in X-ray fluorescence (XRF). It consists of minimizing the differences between an experimental X-ray spectrum and a function proposed to account for the characteristic peaks and background spectrum from the corresponding sample, as well as for detection artifacts. The algorithm starts from some initial values for the different parameters involved, and a numerical iterative procedure produces improved values for them. After the general aspects of the method for refining XRF parameters are presented, a simple application is given for spectra measured in metallic samples with a monochromatic beam from a synchrotron source. In this case, the optimization algorithm is used for the determination of relative transition probabilities for the K shell. Copyright (C) 2002 John Wiley Sons, Ltd.