State-Dependent Electron Delocalization Dynamics at the Solute-Solvent Interface: Soft-X-Ray Absorption Spectroscopy and Ab Initio Calculations

Abstract

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.