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

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 K _α and Co ²⁺ L _l(3s → 2p _3/2), L _η(3s → 2p _1/2), L _α(3d → 2p _3/2) and L _β(3d → 2p _1/2) -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.