Imaging ultrafast excited state pathways in transition metal complexes by X-ray transient absorption and scattering using X-ray free electron laser source

Research output: Contribution to journalJournal article – Annual report year: 2016Researchpeer-review

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  • Author: Chen, Lin X.

    Northwestern University, United States

  • Author: Shelby, Megan L.

    Northwestern University, United States

  • Author: Lestrange, Patrick J

    University of Washington, United States

  • Author: Jackson, Nicholas E

    Northwestern University, United States

  • Author: Haldrup, Kristoffer

    Neutrons and X-rays for Materials Physics, Department of Physics, Technical University of Denmark, Fysikvej, 2800, Kgs. Lyngby, Denmark

  • Author: Mara, Michael W.

    Northwestern University, United States

  • Author: Stickrath, Andrew B.

    Argonne National Laboratory, United States

  • Author: Zhu, Diling

    SLAC National Accelerator Laboratory, United States

  • Author: Lemke, Henrik T.

    SLAC National Accelerator Laboratory, United States

  • Author: Chollet, Matthieu

    SLAC National Accelerator Laboratory, United States

  • Author: Hoffman, Brian M

    Northwestern University, United States

  • Author: Li, Xiaosong

    University of Washington, United States

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This report will describe our recent studies of transition metal complex structural dynamics on the fs and ps time scales using an X-ray free electron laser source, Linac Coherent Light Source (LCLS). Ultrafast XANES spectra at the Ni K-edge of nickel(ii) tetramesitylporphyrin (NiTMP) were measured for optically excited states at a timescale from 100 fs to 50 ps, providing insight into its sub-ps electronic and structural relaxation processes. Importantly, a transient reduced state Ni(i) (π, 3dx2-y2) electronic state is captured through the interpretation of a short-lived excited state absorption on the low-energy shoulder of the edge, which is aided by the computation of X-ray transitions for postulated excited electronic states. The observed and computed inner shell to valence orbital transition energies demonstrate and quantify the influence of the electronic configuration on specific metal orbital energies. A strong influence of the valence orbital occupation on the inner shell orbital energies indicates that one should not use the transition energy from 1s to other orbitals to draw conclusions about the d-orbital energies. For photocatalysis, a transient electronic configuration could influence d-orbital energies up to a few eV and any attempt to steer the reaction pathway should account for this to ensure that external energies can be used optimally in driving desirable processes. NiTMP structural evolution and the influence of the porphyrin macrocycle conformation on relaxation kinetics can be likewise inferred from this study.
Original languageEnglish
JournalFaraday Discussions
Volume194
Pages (from-to)639-658
Number of pages20
ISSN1359-6640
DOIs
Publication statusPublished - 2016
CitationsWeb of Science® Times Cited: No match on DOI

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