1301.6858 (Sergey I. Bokarev et al.)

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

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

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.

View original: http://arxiv.org/abs/1301.6858