TY  - JOUR
A1  - Kunnus, Kristjan
A1  - Zhang, Wenkai
A1  - Delcey, Mickael G.
A1  - Pinjari, Rahul V.
A1  - Miedema, Piter S.
A1  - Schreck, Simon
A1  - Quevedo, Wilson
A1  - Schröder, Henning
A1  - Föhlisch, Alexander
A1  - Gaffney, Kelly J.
A1  - Lundberg, Marcus
A1  - Odelius, Michael
A1  - Wernet, Philippe
T1  - Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives
JF  - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry
N2  - The valence-excited states of ferric and ferrous hexacyanide ions in aqueous solution were mapped by resonant inelastic X-ray scattering (RIXS) at the Fe L-2,L-3 and N K edges. Probing of both the central Fe and the ligand N atoms enabled identification of the metal-and ligand-centered excited states, as well as ligand-to-metal and metal-to-ligand charge-transfer excited states. Ab initio calculations utilizing the RASPT2 method were used to simulate the Fe L-2,L-3-edge RIXS spectra and enabled quantification of the covalencies of both occupied and empty orbitals of pi and sigma symmetry. We found that pi back-donation in the ferric complex is smaller than that in the ferrous complex. This is evidenced by the relative amounts of Fe 3d character in the nominally 2 pi CN- molecular orbital of 7% and 9% in ferric and ferrous hexacyanide, respectively. Utilizing the direct sensitivity of Fe L-3-edge RIXS to the Fe 3d character in the occupied molecular orbitals, we also found that the donation interactions are dominated by sigma bonding. The latter was found to be stronger in the ferric complex, with an Fe 3d contribution to the nominally 5 sigma CN- molecular orbitals of 29% compared to 20% in the ferrous complex. These results are consistent with the notion that a higher charge at the central metal atom increases donation and decreases back-donation.
Y1  - 2016
U6  - https://doi.org/10.1021/acs.jpcb.6b04751
SN  - 1520-6106
VL  - 120
SP  - 7182
EP  - 7194
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Schreck, Simon
A1  - Pietzsch, Annette
A1  - Kennedy, Brian
A1  - Sathe, Conny
A1  - Miedema, Piter S.
A1  - Techert, Simone
A1  - Strocov, Vladimir N.
A1  - Schmitt, Thorsten
A1  - Hennies, Franz
A1  - Rubensson, Jan-Erik
A1  - Föhlisch, Alexander
T1  - Ground state potential energy surfaces around selected atoms from resonant inelastic x-ray scattering
JF  - Scientific reports
N2  - Thermally driven chemistry as well as materials’ functionality are determined by the potential energy surface of a systems electronic ground state. This makes the potential energy surface a central and powerful concept in physics, chemistry and materials science. However, direct experimental access to the potential energy surface locally around atomic centers and to its long-range structure are lacking. Here we demonstrate how sub-natural linewidth resonant inelastic soft x-ray scattering at vibrational resolution is utilized to determine ground state potential energy surfaces locally and detect long-range changes of the potentials that are driven by local modifications. We show how the general concept is applicable not only to small isolated molecules such as O2 but also to strongly interacting systems such as the hydrogen bond network in liquid water. The weak perturbation to the potential energy surface through hydrogen bonding is observed as a trend towards softening of the ground state potential around the coordinating atom. The instrumental developments in high resolution resonant inelastic soft x-ray scattering are currently accelerating and will enable broad application of the presented approach. With this multidimensional potential energy surfaces that characterize collective phenomena such as (bio)molecular function or high-temperature superconductivity will become accessible in near future.
Y1  - 2016
U6  - https://doi.org/10.1038/srep20054
SN  - 2045-2322
VL  - 6
PB  - Nature Publ. Group
CY  - London
ER  -