Monitoring the Evolution of Relative Product Populations at Early Times during a Photochemical Reaction
Year: 2024
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps toward understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species among the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5 H )-thiophenone. This strategy provides experimental validation of the predicted high (∼50%) yield of an episulfide isomer containing a strained three-membered ring within ∼1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.
DOI: 10.1021/jacs.3c13046
Authors: Joao Pedro Figueira Nunes, Lea Maria Ibele, Shashank Pathak, Andrew R. Attar, Surjendu Bhattacharyya, Rebecca Boll, Kurtis Borne, Martin Centurion, Benjamin Erk, Ming-Fu Lin, Ruaridh J. G. Forbes, Nathan Goff, Christopher S. Hansen, Matthias Hoffmann, David M. P. Holland, Rebecca A. Ingle, Duan Luo, Sri Bhavya Muvva, Alexander H. Reid, Arnaud Rouzée, Artem Rudenko, Sajib Kumar Saha, Xiaozhe Shen, Anbu Selvam Venkatachalam, Xijie Wang, Matt R. Ware, Stephen P. Weathersby, Kyle Wilkin, Thomas J. A. Wolf, Yanwei Xiong, Jie Yang, Michael N. R. Ashfold, Daniel Rolles, Basile F. E. Curchod
Institutions: University of Nebraska–Lincoln, Centre National de la Recherche Scientifique, Université Paris-Saclay, Institut de Chimie Physique, Kansas State University, SLAC National Accelerator Laboratory, European X-Ray Free-Electron Laser, Deutsches Elektronen-Synchrotron DESY, Brown University, UNSW Sydney, Daresbury Laboratory, University College London, Max-Born-Institute for Nonlinear Optics and Short Pulse Spectroscopy, University of Bristol
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Funders: National Science Foundation, U.S. Department of Energy, Durham University, Agence Nationale de la Recherche, Office of Science, Horizon 2020 Framework Programme, Engineering and Physical Sciences Research Council, Science and Technology Facilities Council, Australian Research Council, Division of Physics, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, SLAC National Accelerator Laboratory
Awards: G1229526393, G1285540439, G1286236842, G1286251239, G1451874870, G1463467456, G1815137805, Chemical Applications of Velocity and Spatial Imaging, G2181953994, G2197341383, G222768804, G2371548206, G262532246, Ultrafast Photochemical Dynamics in Complex Environments, STRUCTURE AND DYNAMICS OF ATOMS, IONS, MOLECULES AND SURFACES, G303061748, G30714459, G333714909, Quantum Decoherence in Light-induced Charge Transfer Phenomena, G3826261775, G4101533273, G419881185, G4235786860, G42916606, INVESTIGATING CHARGE TRANSFER AND CHARGE MIGRATION ON THE FEW- TO SUB-FEMTOSECOND TIME SCALE, G4580710395, G495301720, G498139845, A Universal Approach for Solving Real-World Problems Using Quantum Dynamics: Coherent States for Molecular Simulations (COSMOS), G5486038727, G5570207115, G5648016710, DTP 2018-19 Durham University, The true impact of fluorinated compounds in the atmosphere, G5941298888, G5993526748, G6315639276, G650090426, G6550344761, ATOMIC PHYSICS WITH HIGHLY CHARGED IONS, G7283024673, G7331630580, STRUCTURAL MOLECULAR DYNAMICS USING ULTRAFAST GAS X-RAY SCATTERING, PROBING NUCLEAR AND ELECTRONIC DYNAMICS IN ULTRAFAST RING-CONVERSION MOLECULAR REACTIONS, CAREER: Investigating Ultrafast Electronic and Structural Dynamics During Light-Driven Chemical Reactions, G786475436, G8067403712, G8382000481, G8395316192, PROBING NUCLEAR AND ELECTRONIC DYNAMICS IN ULTRAFAST RING-CONVERSION MOLECULAR REACTIONS, G911061179, G969889393, STRUCTURE AND DYNAMICS OF ATOMS, IONS, MOLECULES AND SURFACES
OpenAlex ID: W4391568136