Filters

20191

More filters

20211
Reset filters

Settings

DDC: 540 × Publisher: Weinheim : Wiley-VCH × Subject: density functional calculations × WGL Institute: MBI ×

Search Results

Now showing 1 - 1 of 1
  • Thumbnail Image
    Item
    Covalency-Driven Preservation of Local Charge Densities in a Metal-to-Ligand Charge-Transfer Excited Iron Photosensitizer
    (Weinheim : Wiley-VCH, 2019) Jay, Raphael M.; Eckert, Sebastian; Vaz da Cruz, Vinicius; Fondell, Mattis; Mitzner, Rolf; Föhlisch, Alexander
    Covalency is found to even out charge separation after photo-oxidation of the metal center in the metal-to-ligand charge-transfer state of an iron photosensitizer. The σ-donation ability of the ligands compensates for the loss of iron 3d electronic charge, thereby upholding the initial metal charge density and preserving the local noble-gas configuration. These findings are enabled through element-specific and orbital-selective time-resolved X-ray absorption spectroscopy at the iron L-edge. Thus, valence orbital populations around the central metal are directly accessible. In conjunction with density functional theory we conclude that the picture of a localized charge-separation is inadequate. However, the unpaired spin density provides a suitable representation of the electron–hole pair associated with the electron-transfer process. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.