TY  - JOUR
A1  - Jay, Raphael M.
A1  - Vaz da Cruz, Vinicius
A1  - Eckert, Sebastian
A1  - Fondell, Mattis
A1  - Mitzner, Rolf
A1  - Föhlisch, Alexander
T1  - Probing solute-solvent interactions of transition metal complexes using L-edge absorption spectroscopy
JF  - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry
N2  - In order to tailor solution-phase chemical reactions involving transition metal complexes, it is critical to understand how their valence electronic charge distributions are affected by the solution environment. Here, solute-solvent interactions of a solvatochromic mixed-ligand iron complex were investigated using X-ray absorption spectroscopy at the transition metal L-2,L-3-edge. Due to the selectivity of the corresponding core excitations to the iron 3d orbitals, the method grants direct access to the valence electronic structure around the iron center and its response to interactions with the solvent environment. A linear increase of the total L-2,L-3-edge absorption cross section as a function of the solvent Lewis acidity is revealed. The effect is caused by relative changes in different metal-ligand-bonding channels, which preserve local charge densities while increasing the density of unoccupied states around the iron center. These conclusions are corroborated by a combination of molecular dynamics and spectrum simulations based on time-dependent density functional theory. The simulations reproduce the spectral trends observed in the X-ray but also optical absorption experiments. Our results underscore the importance of solute-solvent interactions when aiming for an accurate description of the valence electronic structure of solvated transition metal complexes and demonstrate how L-2,L-3-edge absorption spectroscopy can aid in understanding the impact of the solution environment on intramolecular covalency and the electronic charge distribution.
KW  - basis-sets
KW  - charge-transfer
KW  - density
KW  - dynamics
KW  - electron localization
KW  - iron
KW  - solvation
KW  - spin-crossover
KW  - tranfer excited-state
KW  - x-ray-absorption
Y1  - 2020
U6  - https://doi.org/10.1021/acs.jpcb.0c00638
SN  - 1520-6106
SN  - 1520-5207
VL  - 124
IS  - 27
SP  - 5636
EP  - 5645
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - GEN
A1  - Norell, Jesper
A1  - Jay, Raphael Martin
A1  - Hantschmann, Markus
A1  - Eckert, Sebastian
A1  - Guo, Meiyuan
A1  - Gaffney, Kelly J.
A1  - Wernet, Philippe
A1  - Lundberg, Marcus
A1  - Föhlisch, Alexander
A1  - Odelius, Michael
T1  - Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species
T2  - Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe
N2  - We describe how inversion symmetry separation of electronic state manifolds in resonant inelastic soft X-ray scattering (RIXS) can be applied to probe excited-state dynamics with compelling selectivity. In a case study of Fe L-3-edge RIXS in the ferricyanide complex Fe(CN)(6)(3-), we demonstrate with multi-configurational restricted active space spectrum simulations how the information content of RIXS spectral fingerprints can be used to unambiguously separate species of different electronic configurations, spin multiplicities, and structures, with possible involvement in the decay dynamics of photo-excited ligand-to-metal charge-transfer. Specifically, we propose that this could be applied to confirm or reject the presence of a hitherto elusive transient Quartet species. Thus, RIXS offers a particular possibility to settle a recent controversy regarding the decay pathway, and we expect the technique to be similarly applicable in other model systems of photo-induced dynamics.
T3  - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 779 
KW  - charge-transfer
KW  - relaxation dynamics
KW  - absorption-spectra
KW  - energy-conversion
KW  - basis-sets
KW  - ab-initio
KW  - complexes
KW  - photoelectron
KW  - spectroscopy
KW  - simulations
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-437493
SN  - 1866-8372
IS  - 779
SP  - 7243
EP  - 7253
ER  -