On the origin of dips in total fluorescence yield X-ray absorption spectra: Partial and inverse partial fluorescence yield at the L-edge of cobalt aqueous solution

Abstract

Dips appearing in the L-edge total fluorescence yield (TFY) spectra of transition-metal ions in aqueous solutions have been recently attributed to, orbital mixing of the solute with the solvent orbitals. Here we compare the L-edge TFY, Oxygen Kα and Co2+ Ll(3s→2p3/2), Lη(3s→2p1/2), Lα(3d→2p3/2) and Lβ(3d→2p1/2) –edge partial fluorescence yield with the transmission spectrum. We thereby confirm that these mixed orbitals lead to electron delocalization between the valence d-orbitals of the transition metal and the valence bands of the solvent molecules, quenching their X-ray fluorescence.