Joint Analysis of Radiative and Non-Radiative Electronic Relaxation Upon X-ray Irradiation of Transition Metal Aqueous Solutions.
L-edge soft X-ray spectroscopy has been proven to be a powerful tool to unravel the peculiarities of electronic structure of transition metal compounds in solution. However, the X-ray absorption spectrum is often probed in the total or partial fluorescence yield modes, what leads to inherent distortions with respect to the true transmission spectrum. In the present work, we combine photon- and electron-yield experimental techniques with multi-reference first principles calculations. Exemplified for the prototypical FeCl2 aqueous solution we demonstrate that the partial yield arising from the Fe3s → 2p relaxation is a more reliable probe of the absorption spectrum than the Fe3d → 2p one. For the bonding-relevant 3d → 2p channel we further provide the basis for the joint analysis of resonant photoelectron and inelastic X-ray scattering spectra. Establishing the common energy reference allows to assign both spectra using the complementary information provided through electron-out and photon-out events.
Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Straße 15, D-12489 Berlin, Germany.|Department of Chemistry, Freie Universität Berlin, Takustraße 3, D-14159 Berlin, Germany.
Ronny
R
Golnak
Institut für Physik, Universität Rostock, D-18051 Rostock, Germany.
Sergey I
SI
Bokarev
Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Straße 15, D-12489 Berlin, Germany.
Robert
R
Seidel
Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Straße 15, D-12489 Berlin, Germany.
Jie
J
Xiao
Institut für Physik, Universität Rostock, D-18051 Rostock, Germany.
Gilbert
G
Grell
Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Straße 15, D-12489 Berlin, Germany.
Kaan
K
Atak
Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Straße 15, D-12489 Berlin, Germany.
Isaak
I
Unger
Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-Ku, Kyoto 606-8502, Japan.
Stephan
S
Thürmer
Chemistry Department, Faculty of Science, King Abdulaziz University, 21589 Jeddah, Saudi Arabia.
Saadullah G
SG
Aziz
Institut für Physik, Universität Rostock, D-18051 Rostock, Germany.
Oliver
O
Kühn
Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Straße 15, D-12489 Berlin, Germany.
Bernd
B
Winter
Institute of Methods for Material Development, Helmholtz-Zentrum Berlin, Albert-Einstein-Straße 15, D-12489 Berlin, Germany.|Department of Physics, Freie Universität Berlin, Arnimallee 14, D-14159 Berlin, Germany.
Emad F
EF
Aziz