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Revealing Excited-State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time.
Leshchev, Denis; J S Valentine, Andrew; Kim, Pyosang; Mills, Alexis W; Roy, Subhangi; Chakraborty, Arnab; Biasin, Elisa; Haldrup, Kristoffer; Hsu, Darren J; Kirschner, Matthew S; Rimmerman, Dolev; Chollet, Matthieu; Glownia, J Michael; van Driel, Tim B; Castellano, Felix N; Li, Xiaosong; Chen, Lin X.
Afiliação
  • Leshchev D; Department of Chemistry, Northwestern University, IL 60208, Evanston, USA.
  • J S Valentine A; Department of Chemistry, University of Washington, WA 98195, Seattle, USA.
  • Kim P; Department of Chemistry, Northwestern University, IL 60208, Evanston, USA.
  • Mills AW; Chemical Science and Engineering Division, Argonne National Laboratory, IL 60439, Lemont, USA.
  • Roy S; Department of Chemistry, University of Washington, WA 98195, Seattle, USA.
  • Chakraborty A; Department of Chemistry, North Carolina State University, NC 27695-8204, Raleigh, USA.
  • Biasin E; Department of Chemistry, North Carolina State University, NC 27695-8204, Raleigh, USA.
  • Haldrup K; Physical Sciences Division, Pacific Northwest National Laboratory, WA 99352, Richland, USA.
  • Hsu DJ; Physics Department, Technical University of Denmark, 2800 Kongens, Lyngby, Denmark.
  • Kirschner MS; Department of Chemistry, Northwestern University, IL 60208, Evanston, USA.
  • Rimmerman D; Department of Chemistry, Northwestern University, IL 60208, Evanston, USA.
  • Chollet M; Department of Chemistry, Northwestern University, IL 60208, Evanston, USA.
  • Glownia JM; SLAC National Accelerator Laboratory, Stanford University, CA 94025, Menlo Park, USA.
  • van Driel TB; SLAC National Accelerator Laboratory, Stanford University, CA 94025, Menlo Park, USA.
  • Castellano FN; SLAC National Accelerator Laboratory, Stanford University, CA 94025, Menlo Park, USA.
  • Li X; Department of Chemistry, North Carolina State University, NC 27695-8204, Raleigh, USA.
  • Chen LX; Department of Chemistry, University of Washington, WA 98195, Seattle, USA.
Angew Chem Int Ed Engl ; 62(28): e202304615, 2023 Jul 10.
Article em En | MEDLINE | ID: mdl-37114904
ABSTRACT
Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited-state trajectories of a diplatinum complex featuring photo-activated metal-metal σ-bond formation and associated Pt-Pt stretching motions were detected in real time using femtosecond wide-angle X-ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt-Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited-state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non-equilibrium processes along excited-state trajectories involving multiple excited-state PESs.
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2023 Tipo de documento: Article
Texto completo
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Texto completo: 1 Base de dados: MEDLINE Idioma: En Ano de publicação: 2023 Tipo de documento: Article