TY  - JOUR
A1  - Kunnus, Kristjan
A1  - Josefsson, I.
A1  - Schreck, Simon Frederik
A1  - Quevedo, W.
A1  - Miedema, P. S.
A1  - Techert, S.
A1  - de Groot, F. M. F.
A1  - Föhlisch, Alexander
A1  - Odelius, M.
A1  - Wernet, Ph.
T1  - Quantifying covalent interactions with resonant inelastic soft X-ray scattering
BT  - case study of Ni2+ aqua complex
JF  - Chemical physics letters
N2  - We analyze the effects of covalent interactions in Ni 2p3d resonant inelastic X-ray scattering (RIXS) spectra from aqueous Ni2+ ions and find that the relative RIXS intensities of ligand-to-metal charge-transfer final states with respect to the ligand-field final states reflect the covalent mixing between Ni 3d and water orbitals. Specifically, the experimental intensity ratio at the Ni L-3-edge allows to determine that the Ni 3d orbitals have on average 5.5% of water character. We propose that 2p3d RIXS at the Ni L-3-edge can be utilized to quantify covalency in Ni complexes without the use of external references or simulations.
KW  - Transition-metal ion
KW  - Aqueous solution
KW  - Covalent interaction
KW  - Resonant inelastic X-ray scattering
KW  - Ligand-field state
KW  - Charge-transfer state
Y1  - 2016
U6  - https://doi.org/10.1016/j.cplett.2016.12.046
SN  - 0009-2614
SN  - 1873-4448
VL  - 669
SP  - 196
EP  - 201
PB  - Elsevier
CY  - Amsterdam
ER  - 
TY  - JOUR
A1  - Wernet, Philippe
A1  - Leitner, T.
A1  - Josefsson, Ida
A1  - Mazza, T.
A1  - Miedema, P. S.
A1  - Schroder, H.
A1  - Beye, Martin
A1  - Kunnus, K.
A1  - Schreck, S.
A1  - Radcliffe, P.
A1  - Dusterer, S.
A1  - Meyer, M.
A1  - Odelius, Michael
A1  - Fohlisch, Alexander
T1  - Communication: Direct evidence for sequential dissociation of gas-phase Fe(CO)(5) via a singlet pathway upon excitation at 266 nm
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - We prove the hitherto hypothesized sequential dissociation of Fe(CO)(5) in the gas phase upon photoexcitation at 266 nm via a singlet pathway with time-resolved valence and core-level photoelectron spectroscopy with an x-ray free-electron laser. Valence photoelectron spectra are used to identify free CO molecules and to determine the time constants of stepwise dissociation to Fe(CO)(4) within the temporal resolution of the experiment and further to Fe(CO)(3) within 3 ps. Fe 3p core-level photoelectron spectra directly reflect the singlet spin state of the Fe center in Fe(CO)(5), Fe(CO)(4), and Fe(CO)(3) showing that the dissociation exclusively occurs along a singlet pathway without triplet-state contribution. Our results are important for assessing intra- and intermolecular relaxation processes in the photodissociation dynamics of the prototypical Fe(CO)(5) complex in the gas phase and in solution, and they establish time-resolved core-level photoelectron spectroscopy as a powerful tool for determining the multiplicity of transition metals in photochemical reactions of coordination complexes. Published by AIP Publishing.
Y1  - 2017
U6  - https://doi.org/10.1063/1.4984774
SN  - 0021-9606
SN  - 1089-7690
VL  - 146
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Miedema, P. S.
A1  - Mitzner, Rolf
A1  - Ganschow, S.
A1  - Föhlisch, Alexander
A1  - Beye, Martin
T1  - X-ray spectroscopy on the active ion in laser crystals
JF  - Physical chemistry, chemical physics : a journal of European Chemical Societies
N2  - The active ions in typical laser crystals were studied with Resonant Inelastic X-ray Scattering (RIXS) and Partial Fluorescence Yield X-ray Absorption (PFY-XAS) spectroscopies as solid state model systems for dilute active centers. We analyzed Ti3+ and Cr3+ in alpha-Al2O3:Ti3+ and LiCaAlF6:Cr3+, respectively. The comparison of experimental data with semi-empirical multiplet calculations provides insights into the electronic structure and shows how measured crystal field energies are related across different spectroscopies.
Y1  - 2017
U6  - https://doi.org/10.1039/c7cp03026f
SN  - 1463-9076
SN  - 1463-9084
VL  - 19
SP  - 21800
EP  - 21806
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  -