title: X-ray spectroscopic study of solvent effects on the ferrous and ferric hexacyanide anions.
abstract: We present an Fe Kα resonant inelastic X-ray scattering (RIXS) and X-ray emission (XES) study of ferrous and ferric hexacyanide dissolved in water and ethylene glycol. We observe that transitions below the absorption edge show that the solvent has a distinct effect on the valence electronic structure. In addition, both the RIXS and XES spectra show a stabilization of the 2p levels when dissolved in water. Using molecular dynamics simulations, we propose that this effect arises from the hydrogen-bonding interactions between the complex and nearby solvent molecules. This withdraws electron density from the ligands, stabilizing the complex but also causing a slight increase in π-backbonding.
authors.affiliation: SwissFEL, Paul Scherrer Institute , CH-5232 Villigen, Switzerland.
authors.forename: T J
authors.initials: TJ
authors.lastname: Penfold
authors.forename: M
authors.initials: M
authors.lastname: Reinhard
authors.forename: M H
authors.initials: MH
authors.lastname: Rittmann-Frank
authors.forename: I
authors.initials: I
authors.lastname: Tavernelli
authors.forename: U
authors.initials: U
authors.lastname: Rothlisberger
authors.forename: C J
authors.initials: CJ
authors.lastname: Milne
authors.forename: P
authors.initials: P
authors.lastname: Glatzel
authors.forename: M
authors.initials: M
authors.lastname: Chergui