Extraction of EELS white-line intensities of manganese compounds: methods, accuracy, and valence sensitivity.

This article evaluates the valence sensitivity and accuracy of selected EELS white-line extraction methods based on the white-line intensity ratio in case of manganese oxides, predominantly in the valency range [Mn3+ ; Mn4+]. For this purpose Mn-L2,3 ionization edges of several Mn oxides were measured and four different methods were applied to extract the intensities. The obtained ratios have been analyzed in terms of their errors, their scatter, and their sensitivity on manganese valency. We found that the maximum-intensity as well as the Pearson and Walsh-Dray methods show larger relative changes of the ratio between Mn3+ and Mn4+ than curve-fitting. Taking the scatter into account, Walsh-Dray distinguishes more clearly between those two valencies than curve-fitting. Thus the Walsh-Dray method promises the most accurate determination of small valency shifts.