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

Sergey I. Bokarev, Marcus Dantz, Edlira Suljoti, Oliver Kühn, Emad F. Aziz

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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.

Original languageEnglish
Article number083002
JournalPhysical Review Letters
Issue number8
Publication statusPublished - 20 Aug 2013
Externally publishedYes

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