Nonradiative decay channels in the L-edge fluorescence yield spectra from
transition-metal–aqueous solutions give rise to spectral distortions with
respect to x-ray transmission spectra. Their origin is unraveled here using
partial and inverse partial fluorescence yields on the microjet combined with
multireference ab initio electronic structure calculations. Comparing Fe2+,
Fe3+, and Co2+ systems we demonstrate and quantify unequivocally the state-
dependent electron delocalization within the manifold of d orbitals as one
origin of this observation
