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Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer.
Biasin, Elisa; Fox, Zachary W; Andersen, Amity; Ledbetter, Kathryn; Kjær, Kasper S; Alonso-Mori, Roberto; Carlstad, Julia M; Chollet, Matthieu; Gaynor, James D; Glownia, James M; Hong, Kiryong; Kroll, Thomas; Lee, Jae Hyuk; Liekhus-Schmaltz, Chelsea; Reinhard, Marco; Sokaras, Dimosthenis; Zhang, Yu; Doumy, Gilles; March, Anne Marie; Southworth, Stephen H; Mukamel, Shaul; Gaffney, Kelly J; Schoenlein, Robert W; Govind, Niranjan; Cordones, Amy A; Khalil, Munira.
Afiliación
  • Biasin E; Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA. ebiasin@stanford.edu.
  • Fox ZW; Department of Chemistry, University of Washington, Seattle, WA, USA.
  • Andersen A; Environmental Molecular Sciences Division, Earth and Biological Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA, USA.
  • Ledbetter K; Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Kjær KS; Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Alonso-Mori R; Department of Physics, Technical University of Denmark, Kongens Lyngby, Denmark.
  • Carlstad JM; Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Chollet M; Department of Chemistry, University of Washington, Seattle, WA, USA.
  • Gaynor JD; Department of Chemistry, University of California, Berkeley, CA, USA.
  • Glownia JM; Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Hong K; Department of Chemistry, University of Washington, Seattle, WA, USA.
  • Kroll T; Department of Chemistry, University of California, Berkeley, CA, USA.
  • Lee JH; Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Liekhus-Schmaltz C; Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
  • Reinhard M; Gas Metrology Group, Division of Chemical and Biological Metrology, Korea Research Institute of Standards and Science, Daejeon, Republic of Korea.
  • Sokaras D; Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Zhang Y; Ultrafast X-ray Science Laboratory, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
  • Doumy G; Pohang Accelerator Laboratory, Pohang, Republic of Korea.
  • March AM; Department of Chemistry, University of Washington, Seattle, WA, USA.
  • Southworth SH; Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Mukamel S; Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, CA, USA.
  • Gaffney KJ; Department of Chemistry, Physics, and Astronomy, University of California, Irvine, CA, USA.
  • Schoenlein RW; Q-Chem, Pleasanton, CA, USA.
  • Govind N; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA.
  • Cordones AA; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA.
  • Khalil M; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA.
Nat Chem ; 13(4): 343-349, 2021 04.
Article en En | MEDLINE | ID: mdl-33589787
ABSTRACT
It is well known that the solvent plays a critical role in ultrafast electron-transfer reactions. However, solvent reorganization occurs on multiple length scales, and selectively measuring short-range solute-solvent interactions at the atomic level with femtosecond time resolution remains a challenge. Here we report femtosecond X-ray scattering and emission measurements following photoinduced charge-transfer excitation in a mixed-valence bimetallic (FeiiRuiii) complex in water, and their interpretation using non-equilibrium molecular dynamics simulations. Combined experimental and computational analysis reveals that the charge-transfer excited state has a lifetime of 62 fs and that coherent translational motions of the first solvation shell are coupled to the back electron transfer. Our molecular dynamics simulations identify that the observed coherent translational motions arise from hydrogen bonding changes between the solute and nearby water molecules upon photoexcitation, and have an amplitude of tenths of ångströms, 120-200 cm-1 frequency and ~100 fs relaxation time. This study provides an atomistic view of coherent solvent reorganization mediating ultrafast intramolecular electron transfer.
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Texto completo: 1 Colección: 01-internacional Banco de datos: MEDLINE Idioma: En Revista: Nat Chem Asunto de la revista: QUIMICA Año: 2021 Tipo del documento: Article País de afiliación: Estados Unidos
Texto completo
Imprimir
XML
PubMed Links
Buscar en Google

Texto completo: 1 Colección: 01-internacional Banco de datos: MEDLINE Idioma: En Revista: Nat Chem Asunto de la revista: QUIMICA Año: 2021 Tipo del documento: Article País de afiliación: Estados Unidos