Distinguishing the XUV-induced Coulomb explosion dynamics of iodobenzene using covariance analysis
Abstract The primary and secondary fragmentation dynamics of iodobenzene following its ionization at 120 eV were determined using three-dimensional velocity map imaging and covariance analysis. Site-selective iodine 4d ionization was used to populate a range of excited polycationic parent states, which primarily broke apart at the carbon-iodine bond to produce I + with phenyl or phenyl-like cations (C n H <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msup> <mml:mrow> <mml:msub> <mml:mrow/> <mml:mi>x</mml:mi> </mml:msub> </mml:mrow> <mml:mo>+</mml:mo> </mml:msup> </mml:mrow> </mml:math> or C n H <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msup> <mml:mrow> <mml:msub> <mml:mrow/> <mml:mi>x</mml:mi> </mml:msub> </mml:mrow> <mml:mrow> <mml:mn>2</mml:mn> <mml:mo>+</mml:mo> </mml:mrow> </mml:msup> </mml:mrow> </mml:math> , with n = 1 – 6 and x = 1 – 5). The molecular products were produced with varying degrees of internal excitation and dehydrogenation, leading to stable and unstable outcomes. This further allowed the secondary dynamics of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mrow> <mml:msub> <mml:mrow> <mml:mi mathvariant="normal">C</mml:mi> </mml:mrow> <mml:mn>6</mml:mn> </mml:msub> <mml:msub> <mml:mrow> <mml:mi mathvariant="normal">H</mml:mi> </mml:mrow> <mml:mi>x</mml:mi> </mml:msub> <mml:msup> <mml:mstyle scriptlevel="0"/> <mml:mrow> <mml:mn>2</mml:mn> <mml:mo>+</mml:mo> </mml:mrow> </mml:msup> </mml:mrow> </mml:math> intermediates to be distinguished using native-frame covariance analysis, which isolated these processes in their own centre-of-mass reference frames. The mass resolution of the imaging mass spectrometer used for these measurements enabled the primary and secondary reaction channels to be specified at the level of individual hydrogen atoms, demonstrating the ability of covariance analysis to comprehensively measure the competing fragmentation channels of aryl cations, including those involving intermediate steps.
Authors
- Daniel Rolles (ORCID: https://orcid.org/0000-0002-3965-3477)
- Felix Allum (ORCID: https://orcid.org/0000-0002-8044-8969)
- Mizuho Fushitani (ORCID: https://orcid.org/0000-0002-1683-0178)
- Weronika O. Razmus
- M. Brouard (ORCID: https://orcid.org/0000-0003-3421-0850)
- P. H. Bucksbaum (ORCID: https://orcid.org/0000-0003-1258-5571)
- Emily M. Warne (ORCID: https://orcid.org/0000-0002-1205-6939)
- Johannes Niskanen (ORCID: https://orcid.org/0000-0002-5501-3082)
- Edwin Kukk (ORCID: https://orcid.org/0000-0001-5275-5913)
- James Unwin (ORCID: https://orcid.org/0000-0001-6009-6735)
- Kiyonobu Nagaya (ORCID: https://orcid.org/0000-0001-9867-0800)
- James Robert Harries (ORCID: https://orcid.org/0000-0003-2173-0697)
- Andrew J. Howard (ORCID: https://orcid.org/0000-0003-0303-3222)
- Ruaridh Forbes (ORCID: https://orcid.org/0000-0003-2097-5991)
- C.C. Lam (ORCID: https://orcid.org/0000-0002-4296-7944)
- Akinobu Niozu (ORCID: https://orcid.org/0000-0002-7292-5630)
- Yoshiaki Kumagai (ORCID: https://orcid.org/0000-0002-2492-4676)
- Mathew Britton
- Russell S. Minns (ORCID: https://orcid.org/0000-0001-6775-2977)
- T. Gejo (ORCID: https://orcid.org/0000-0002-7191-4999)
- Michael Burt (ORCID: https://orcid.org/0000-0002-7317-8649)
- Shigeki Owada (ORCID: https://orcid.org/0000-0002-1451-7612)
- Ian Gabalski (ORCID: https://orcid.org/0000-0002-6782-6566)
- Hiroshi Iwayama (ORCID: https://orcid.org/0000-0002-5992-5281)
- Joseph McManus (ORCID: https://orcid.org/0000-0002-7911-2042)
- Paul Hockett (ORCID: https://orcid.org/0000-0001-9561-8433)
- S. Wada (ORCID: https://orcid.org/0000-0002-6417-3248)
- Tiffany Walmsley (ORCID: https://orcid.org/0000-0002-1446-5904)
- Seung-Lark Lim (ORCID: https://orcid.org/0000-0002-0360-6361)
- Joanne L. Woodhouse (ORCID: https://orcid.org/0000-0002-0771-5362)
- K. Ueda (ORCID: https://orcid.org/0000-0003-0608-0323)
- Sekito Nishimuro
- James Somper
Institutions
- Hiroshima University (JP)
- Tokyo Institute of Technology (JP)
- University of Turku (FI)
- University of Hyogo (JP)
- Kansas State University (US)
- Tohoku University (JP)
- Kyoto University (JP)
- SLAC National Accelerator Laboratory (US)
- University of Oxford (GB)
- SPring-8 (JP)
- Japan Synchrotron Radiation Research Institute (JP)
- National Institutes for Quantum Science and Technology (JP)
- Linac Coherent Light Source (US)
- Institute for Molecular Science (JP)
- National Research Council Canada (CA)
- University of Southampton (GB)
- Nagoya University (JP)
- Tokyo University of Agriculture and Technology (JP)
- Stanford University (US)
Publication Details
- Journal
- Journal of Physics B Atomic Molecular and Optical Physics
- Published
- 2024-10-16
- DOI
- https://doi.org/10.1088/1361-6455/ad8799
- Citations
- 5
- Primary Topic
- Advanced Chemical Physics Studies
- Type
- article
- Field-Weighted Citation Impact
- 1.69
Funders
- U.S. Department of Energy
- Leverhulme Trust
- University of Southampton
- University of Oxford
- Academy of Finland
- Office of Science
- Engineering and Physical Sciences Research Council
- Jesus College, University of Cambridge
- Jesus College, University of Oxford
- Japan Society for the Promotion of Science
- Basic Energy Sciences
- SLAC National Accelerator Laboratory