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-alpha and Co2+ L-l(3s --> 2p(3/2)), L-eta(3s --> 2p(1/2)), L-alpha(3d --> 2p(3/2)) and L-beta(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. (C) 2012 Elsevier B.V. All rights reserved.