Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy

Research output: Contribution to journalJournal article – Annual report year: 2017Researchpeer-review

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  • Author: March, Anne Marie

    Argonne National Laboratory, United States

  • Author: Assefa, Tadesse A.

    European XFEL, Germany

  • Author: Boemer, Christina

    European XFEL, Germany

  • Author: Bressler, Christian

    European XFEL, Germany

  • Author: Britz, Alexander

    European XFEL, Germany

  • Author: Diez, Michael

    European XFEL, Germany

  • Author: Doumy, Gilles

    Argonne National Laboratory, United States

  • Author: Galler, Andreas

    European XFEL, Germany

  • Author: Harder, Manuel

    Deutsches Elektronen-Synchrotron, Germany

  • Author: Khakhulin, Dmitry

    European XFEL, Germany

  • Author: Németh, Zoltán

    Hungarian Academy of Sciences, Hungary

  • Author: Pápai, Mátyás Imre

    Department of Chemistry, Technical University of Denmark, Kemitorvet, 2800, Kgs. Lyngby, Denmark

  • Author: Schulz, Sebastian

    European XFEL, Germany

  • Author: Southworth, Stephen H.

    Argonne National Laboratory, United States

  • Author: Yavas, Hasan

    Deutsches Elektronen-Synchrotron, Germany

  • Author: Young, Linda

    Argonne National Laboratory, United States

  • Author: Gawelda, Wojciech

    European XFEL, Germany

  • Author: Vanko, Gyorgy

    Hungarian Academy of Sciences, Hungary

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We probe the dynamics of valence electrons in photoexcited [Fe(terpy)2]2+ in solution to gain deeper insight into the Fe ligand bond changes. We use hard X-ray emission spectroscopy (XES), which combines element specificity and high penetration with sensitivity to orbital structure, making it a powerful technique for molecular studies in a wide variety of environments. A picosecond-time-resolved measurement of the complete Is X-ray emission spectrum captures the transient photoinduced changes and includes the weak valence-to-core (vtc) emission lines that correspond to transitions from occupied valence orbitals to the nascent core-hole. Vtc-XES offers particular insight into the molecular orbitals directly involved in the light-driven dynamics; a change in the metal ligand orbital overlap results in an intensity reduction and a blue energy shift in agreement with our theoretical calculations and more subtle features at the highest energies reflect changes in the frontier orbital populations.
Original languageEnglish
JournalJournal of Physical Chemistry C
Volume121
Issue number5
Pages (from-to)2620-2626
ISSN1932-7447
DOIs
Publication statusPublished - 2017
CitationsWeb of Science® Times Cited: No match on DOI

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