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Electronic relaxation, the change in molecular electronic structure as a response to oxidation, is investigated in [FeX4]2-,1- (X = Cl, SR) model complexes. Photoelectron spectroscopy, in conjunction with density functional methods, is used to define and evaluate the core and valence electronic relaxation upon ionization of [FeX4]2-. The presence of intense yet formally forbidden charge-transfer satellite peaks in the PES data is a direct reflection of electronic relaxation. The phenomenon is evaluated as a function of charge redistribution at the metal center (Δqrlx) resulting from changes in the electronic structure.

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It is found that electronic relaxation is very large for both core (Fe 2p) and valence (Fe 3d) ionization processes and that it is greater in [Fe(SR)4]2- than in [FeCl4]2-.

What is Photoelectron spectroscopy?

  • When attempting to ascertain the various positions of an electron within an atom, the term "photoelectron spectroscopy" refers to a specific sort of spectroscopic technique. Because of this, when examining the valence shell, it is necessary to consider the electron's ionisation energy.
  • By measuring the relative energy of electrons in atoms and molecules, the experimental method of photoelectron spectroscopy (PES) is used. PES is frequently used by scientists to examine the atomic structure of materials or to describe molecular bonding.
  • UV photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy are typically used as the field's two arbitrary classifications (XPS). The names are based on the energy of the photons that were used in that specific spectroscopy.

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