Revealing Excited-State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Denis Leshchev, Andrew J. S. Valentine, Pyosang Kim, Alexis W. Mills, Subhangi Roy, Arnab Chakraborty, Elisa Biasin, Kristoffer Haldrup, Darren J. Hsu, Matthew S. Kirschner, Dolev Rimmerman, Matthieu Chollet, J. Michael Glownia, Tim B. van Driel, Felix N. Castellano*, Xiaosong Li*, Lin X. Chen*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

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.

Original languageEnglish (US)
Article numbere202304615
JournalAngewandte Chemie - International Edition
Volume62
Issue number28
DOIs
StatePublished - Jul 10 2023

Keywords

  • Excited States
  • Intersystem Crossing
  • Platinum
  • Transition-Metal Complexes
  • Ultrafast Spectroscopy

ASJC Scopus subject areas

  • General Chemistry
  • Catalysis

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