Non-radiative decay channels in the L-edge fluorescence spectra from transition metal-aqueous solutions give rise to spectral dips in X-ray transmission spectra. Their origin is unraveled here using partial and inverse partial fluorescence yields on the micro-jet combined with multi-reference ab initio electronic structure calculations. Comparing Fe2+, Fe3+, and Co2+ systems we demonstrate unequivocally that spectral dips are due to a state-dependent electron delocalization within the manifold of d-orbitals.
@article{arxiv.1301.6858,
title = {State-Dependent Electron Delocalization Dynamics at the Solute-Solvent Interface: Soft X-ray Absorption Spectroscopy and Ab Initio Calculations},
author = {Sergey I. Bokarev and Marcus Dantz and Edlira Suljoti and Oliver Kühn and Emad F. Aziz},
journal= {arXiv preprint arXiv:1301.6858},
year = {2015}
}