Description:
<jats:p>The transient electronic and molecular structure arising from photoinduced charge transfer in transition metal complexes is studied by X-ray powder diffraction with a 100 fs temporal and atomic spatial resolution. Crystals containing a dense array of Fe(II)-tris(bipyridine) ([Fe(bpy)3]2 +) complexes and their \documentclass[12pt]{minimal}\begin{document}${\rm PF}_6^{\ -}$\end{document} PF 6− counterions display pronounced changes of electron density that occur within the first 100 fs after two-photon excitation of a small fraction of the [Fe(bpy)3]2 + complexes. Transient electron density maps derived from the diffraction data reveal a transfer of electronic charge from the Fe atoms and—so far unknown—from the \documentclass[12pt]{minimal}\begin{document}${\rm PF}_6^{\ -}$\end{document} PF 6− counterions to the bipyridine units. Such charge transfer (CT) is connected with changes of the inter-ionic and the Fe-bipyridine distances. An analysis of the electron density maps demonstrates the many-body character of charge transfer which affects approximately 30 complexes around a directly photoexcited one. The many-body behavior is governed by the long-range Coulomb forces in the ionic crystals and described by the concept of electronic polarons.</jats:p>