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.

doi:10.1002/ange.202304615

Title: Revealing Excited‐State Trajectories on Potential Energy Surfaces with Atomic Resolution in Real Time

Journal Article · 30 May 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202304615 · OSTI ID:1975869

Leshchev, Denis ^[1]; J. S. Valentine, Andrew ^[2]; Kim, Pyosang ^[3]; Mills, Alexis W. ^[2]; Roy, Subhangi ^[4]; Chakraborty, Arnab ^[4]; Biasin, Elisa ^[5]; Haldrup, Kristoffer ^[6]; Hsu, Darren J. ^[1]; Kirschner, Matthew S. ^[1]; Rimmerman, Dolev ^[1]; Chollet, Matthieu ^[7]; Glownia, J. Michael ^[7]; van Driel, Tim B. ^[7]; Castellano, Felix N. ^[4]; Li, Xiaosong ^[2];

^[3]

Department of Chemistry Northwestern University IL 60208 Evanston USA
Department of Chemistry University of Washington WA 98195 Seattle USA
Department of Chemistry Northwestern University IL 60208 Evanston USA, Chemical Science and Engineering Division Argonne National Laboratory IL 60439 Lemont USA
Department of Chemistry North Carolina State University NC 27695-8204 Raleigh USA
Physical Sciences Division Pacific Northwest National Laboratory WA 99352 Richland USA
Physics Department Technical University of Denmark 2800 Kongens Lyngby Denmark
SLAC National Accelerator Laboratory Stanford University CA 94025 Menlo Park USA

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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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515; SC0006863

OSTI ID:: 1975869

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 28 Vol. 135; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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