Fragmentation dynamics of CS2 dications and trications following S 2p ionization

We present the results from a detailed study of the fragmentation dynamics of CS22+ and CS23+, formed in intense femtosecond soft x-ray pulses above the sulfur 2p edge, primarily through single core photoionization from the S 2p site, and subsequent Auger-Meitner decay(s). By combining three-dimensional velocity map imaging with covariance analysis, we determine the relative momenta of the ions produced in each two- and three-body fragmentation channel, at significantly higher ion count rates than conventional coincidence measurements. We shed new light on the wide range of fragmentation channels observed from the CS2 dication and trication, including channels that involve ionization-induced bond formation and fragmentations producing undetected neutral cofragments. In the latter case, a "native frames" approach is used to isolate contributions from concerted and sequential fragmentations and extract dynamical information about each step of a concerted fragmentation process. While dications often fragment sequentially, the trication is dominated by concerted fragmentation. The main trication fragmentation channel into S+ + C+ + S+ can be well-approximated by classical Coulombic simulations of the ground-state geometry distribution, reflecting both the nature of the trication potential energy surface and the rapid multiple ionization prior to substantial structural dynamics. This study demonstrates ways in which fundamental insights into the fragmentation dynamics of polycations following x-ray ionization may be extracted, which will be beneficial to future studies that employ time-resolved x-ray Coulomb explosion imaging to study ultrafast photochemistry.

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Journal
The Journal of Chemical Physics
Published
2026-01-09
DOI
https://doi.org/10.1063/5.0304278
Primary Topic
Laser-Plasma Interactions and Diagnostics
Type
article
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0.00

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article

Fragmentation dynamics of CS2 dications and trications following S 2p ionization

Arnaud Rouzée, Felix Allum, C. Vallance, Nagitha Ekanayake et al.
The Journal of Chemical Physics
Laser-Plasma Interactions and Diagnostics
article

Fragmentation dynamics of CS2 dications and trications following S 2p ionization

Arnaud Rouzée, Felix Allum, C. Vallance, Nagitha Ekanayake, Weronika O. Razmus, Jason W. L. Lee, M. Brouard, P. H. Bucksbaum, Eva Gougoula, James Unwin, Albert Stolow, Michael S. Schuurman, Dennis Milešević, C.C. Lam, Benjamin Erk, Russell S. Minns, H. Bromberger, Anja Röder, D.M.P. Holland, Ian Gabalski, David Heathcote, C. Passow, Joseph McManus, Tiffany Walmsley, Jochen Mikosch, Sonu Kumar, Paul Hockett, Christina C. Papadopoulou, Atia-Tul Noor, A. D. Howard, Daniel Rolles, Alcides Simao, Diksha Garg, Mathew Britton, Michael Burt
article en

Abstract

We present the results from a detailed study of the fragmentation dynamics of CS22+ and CS23+, formed in intense femtosecond soft x-ray pulses above the sulfur 2p edge, primarily through single core photoionization from the S 2p site, and subsequent Auger-Meitner decay(s). By combining three-dimensional velocity map imaging with covariance analysis, we determine the relative momenta of the ions produced in each two- and three-body fragmentation channel, at significantly higher ion count rates than conventional coincidence measurements. We shed new light on the wide range of fragmentation channels observed from the CS2 dication and trication, including channels that involve ionization-induced bond formation and fragmentations producing undetected neutral cofragments. In the latter case, a "native frames" approach is used to isolate contributions from concerted and sequential fragmentations and extract dynamical information about each step of a concerted fragmentation process. While dications often fragment sequentially, the trication is dominated by concerted fragmentation. The main trication fragmentation channel into S+ + C+ + S+ can be well-approximated by classical Coulombic simulations of the ground-state geometry distribution, reflecting both the nature of the trication potential energy surface and the rapid multiple ionization prior to substantial structural dynamics. This study demonstrates ways in which fundamental insights into the fragmentation dynamics of polycations following x-ray ionization may be extracted, which will be beneficial to future studies that employ time-resolved x-ray Coulomb explosion imaging to study ultrafast photochemistry.

The Journal of Chemical PhysicsVol. 164(2)
University of Kassel (DE), University of Ottawa (CA), Universität Hamburg (DE), Kansas State University (US), Deutsches Elektronen-Synchrotron DESY (DE), SLAC National Accelerator Laboratory (US), Daresbury Laboratory (GB), University of Oxford (GB), Max Planck - University of Ottawa Centre for Extreme and Quantum Photonics (CA), Max-Born-Institute for Nonlinear Optics and Short Pulse Spectroscopy (DE), Linac Coherent Light Source (US), National Research Council Canada (CA), University of Southampton (GB), Trent University (CA), University of California, Davis (US), Ruhr University Bochum (DE), Stanford University (US)
National Science Foundation, U.S. Department of Energy, Alexander von Humboldt-Stiftung, CALIPSOplus, Leverhulme Trust, University of Southampton, Bundesministerium für Bildung und Forschung, Max-Planck-Gesellschaft, Office of Science, National Defense Science and Engineering Graduate, Engineering and Physical Sciences Research Council, Science and Technology Facilities Council, Jesus College, University of Cambridge, Jesus College, University of Oxford, Deutsches Elektronen-Synchrotron, Horizon 2020, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, SLAC National Accelerator Laboratory
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