title: Imaging ultrafast excited state pathways in transition metal complexes by X-ray transient absorption and scattering using X-ray free electron laser source.
abstract: 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.
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois, USA. lchen@anl.gov and Department of Chemistry, Northwestern University, Evanston, Illinois, USA. l-chen@northwestern.edu.
authors.forename: Lin X
authors.initials: LX
authors.lastname: Chen
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois, USA. lchen@anl.gov and Department of Chemistry, Northwestern University, Evanston, Illinois, USA. l-chen@northwestern.edu.
authors.forename: Megan L
authors.initials: ML
authors.lastname: Shelby
authors.affiliation: Department of Chemistry, University of Washington, Seattle, WA 98195, USA.
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Lestrange
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois, USA. lchen@anl.gov and Department of Chemistry, Northwestern University, Evanston, Illinois, USA. l-chen@northwestern.edu.
authors.forename: Nicholas E
authors.initials: NE
authors.lastname: Jackson
authors.affiliation: Physics Department, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark.
authors.forename: Kristoffer
authors.initials: K
authors.lastname: Haldrup
authors.affiliation: Department of Chemistry, Northwestern University, Evanston, Illinois, USA. l-chen@northwestern.edu.
authors.forename: Michael W
authors.initials: MW
authors.lastname: Mara
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois, USA. lchen@anl.gov.
authors.forename: Andrew B
authors.initials: AB
authors.lastname: Stickrath
authors.affiliation: LCLS, SLAC National Laboratory, Menlo Park, CA 94025, USA.
authors.forename: Diling
authors.initials: D
authors.lastname: Zhu
authors.affiliation: LCLS, SLAC National Laboratory, Menlo Park, CA 94025, USA.
authors.forename: Henrik
authors.initials: H
authors.lastname: Lemke
authors.affiliation: LCLS, SLAC National Laboratory, Menlo Park, CA 94025, USA.
authors.forename: Matthieu
authors.initials: M
authors.lastname: Chollet
authors.affiliation: Department of Chemistry, Northwestern University, Evanston, Illinois, USA. l-chen@northwestern.edu.
authors.forename: Brian M
authors.initials: BM
authors.lastname: Hoffman
authors.affiliation: Department of Chemistry, University of Washington, Seattle, WA 98195, USA.
authors.forename: Xiaosong
authors.initials: X
authors.lastname: Li
mesh_terms: D056831:Coordination Complexes; D004583:Electrons; D007834:Lasers; D008968:Molecular Conformation; D011166:Porphyrins / Q000737:chemistry; D011789:Quantum Theory; D014965:X-Rays
chemical_list: D056831:Coordination Complexes; D011166:Porphyrins