Chemical bonding in aqueous ferrocyanide: experimental and theoretical X-ray spectroscopic study.
Resonant inelastic X-ray scattering (RIXS) and X-ray absorption (XA) experiments at the iron L- and nitrogen K-edge are combined with high-level first-principles restricted active space self-consistent field (RASSCF) calculations for a systematic investigation of the nature of the chemical bond in potassium ferrocyanide in aqueous solution. The atom- and site-specific RIXS excitations allow for direct observation of ligand-to-metal (Fe L-edge) and metal-to-ligand (N K-edge) charge-transfer bands and thereby evidence for strong σ-donation and π-backdonation. The effects are identified by comparing experimental and simulated spectra related to both the unoccupied and occupied molecular orbitals in solution.
Joint Ultrafast Dynamics Lab in Solutions and at Interfaces (JULiq) at Helmholtz-Zentrum Berlin für Materialien und Energie , Albert-Einstein-Strasse 15, 12489 Berlin, Germany.
Nicholas
N
Engel
Sergey I
SI
Bokarev
Edlira
E
Suljoti
Raul
R
Garcia-Diez
Kathrin M
KM
Lange
Kaan
K
Atak
Ronny
R
Golnak
Alexander
A
Kothe
Marcus
M
Dantz
Oliver
O
Kühn
Emad F
EF
Aziz