@article{WernetKunnusSchrecketal.2012,
  author    = {Wernet, Philippe and Kunnus, Kristjan and Schreck, Simon and Quevedo, Wilson and Kurian, Reshmi and Techert, Simone and de Groot, Frank M. F. and Odelius, Michael and F{\"o}hlisch, Alexander},
  title     = {Dissecting local atomic and intermolecular interactions of transition-metal ions in solution with selective X-ray spectroscopy},
  series = {The journal of physical chemistry letters},
  volume    = {3},
  journal   = {The journal of physical chemistry letters},
  number    = {23},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {1948-7185},
  doi       = {10.1021/jz301486u},
  pages     = {3448 -- 3453},
  year      = {2012},
  abstract  = {Determining covalent and charge-transfer contributions to bonding in solution has remained an experimental challenge. Here, the quenching of fluorescence decay channels as expressed in dips in the L-edge X-ray spectra of solvated 3d transition-metal ions and complexes was reported as a probe. With a full set of experimental and theoretical ab initio L-edge X-ray spectra of aqueous Cr3+, including resonant inelastic X-ray scattering, we address covalency and charge transfer for this prototypical transition-metal ion in solution. We dissect local atomic effects from intermolecular interactions and quantify X-ray optical effects. We find no evidence for the asserted ultrafast charge transfer to the solvent and show that the dips are readily explained by X-ray optical effects and local atomic state dependence of the fluorescence yield. Instead, we find, besides ionic interactions, a covalent contribution to the bonding in the aqueous complex of ligand-to-metal charge-transfer character.},
  language  = {en}
}