Resonant Stimulated X-ray Raman Spectroscopy of Mixed-Valence Manganese Complexes
Resonant stimulated X-ray Raman spectroscopy of the bimetallic [MnIIIMnIV(μ-O)2(μ-OAC)(tacn)2]2+ manganese complex is investigated in a simulation study. Essential biological processes, including water oxidation in photosynthesis, involve charge transfer between manganese sites of different oxidation states. We study a prototypical binuclear mixed-valence transition-metal complex with two Mn atoms in different oxidation states surrounded by ligand structures and employ a pump-probe sequence of resonant X-ray Raman excitations to follow the charge transfer occurring in the molecule. This allows us to generate and monitor valence-electron wave packets at selected regions in the molecule by exploiting element-specific core-excited states. A two-color protocol is presented, with pump and probe pulses tuned to the Mn and N K-edges. A natural orbital decomposition allows the visualization of the electron dynamics underlying the signal.
Journal of Physical Chemistry Letters
Cavaletto, S., Nascimento, D., Zhang, Y., Govind, N., & Mukamel, S. (2021). Resonant Stimulated X-ray Raman Spectroscopy of Mixed-Valence Manganese Complexes. Journal of Physical Chemistry Letters, 12, 5925-5931. https://doi.org/10.1021/acs.jpclett.1c01190