State-dependent electron delocalization dynamics at the solute-solvent interface: Soft-x-ray absorption spectroscopy and Ab initio calculations

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.