Total 3s Emission Yield as Bulk-Sensitive Probe for a True Soft X-ray Absorption Spectrum?

The detection of the true soft X-ray absorption typically needs specially prepared submicrometer thin samples for transmission measurements. Bulk experiments instead have to rely on yield methods, for example, electron yield with limitations for insulating samples, sensitivity to applied fields, and with limited bulk sensitivity. Fluorescence yield methods instead do not have those limitations but have been found to deviate, in general, from the absorption spectrum. We demonstrate that restricting the detection to the 3s fluorescence channel (with the detector at a special angle where all polarizations contribute equally) restores the true X-ray absorption spectrum for all 3d-metal L edges. These theoretically derived results are rationalized by the lack of 3s-3d interaction in the core-excited state. Comparing X-ray absorption versus 3s-PFY for arbitrary detection geometries for both linear and circular polarized light, deviations appear that can become as large as 15%.