Fragmentation dynamics of CS2 dications and trications following S 2p ionization
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.
Article Details
Journal Info
The Journal of Chemical Physics
American Institute of Physics
Authors (36)
Felix Allum
Stanford PULSE Institute
Chow-shing Lam
Benjamin Erk
Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, Hamburg 22607, Germany
Hubertus Bromberger
Deutsches Elektronen-Synchrotron DESY 1 , Notkestr. 85, 22607 Hamburg,
Philip H. Bucksbaum
Mathew Britton
Michael Burt
Chemistry Research Laboratory, Department of Chemistry
Nagitha Ekanayake
Deutsches Elektronen-Synchrotron DESY 1 , Notkestr. 85, 22607 Hamburg,
Ian Gabalski
Diksha Garg
Deutsches Elektronen-Synchrotron DESY 1 , Notkestr. 85, 22607 Hamburg,
Eva Gougoula
Deutsches Elektronen-Synchrotron DESY 1 , Notkestr. 85, 22607 Hamburg,
David Heathcote
Andrew J. Howard
Paul Hockett
David M. P. Holland
Daresbury Laboratory
Sonu Kumar
Jason W. L. Lee
Joseph McManus
Chemistry Research Laboratory, Department of Chemistry, University of Oxford 4 , Oxford OX1 3TA,
Jochen Mikosch
Institut für Physik, Universität Kassel 12 , Heinrich-Plett-Straße 40, 34132 Kassel,
Dennis Milešević
Chemistry Research Laboratory, Department of Chemistry, University of Oxford 4 , Oxford OX1 3TA,
Russell S. Minns
School of Chemistry and Chemical Engineering
Christina C. Papadopoulou
Deutsches Elektronen-Synchrotron DESY 1 , Notkestr. 85, 22607 Hamburg,
Christopher Passow
Weronika O. Razmus
Anja Röder
Max-Born-Institute 14 , Max-Born-Straße 2A, 12489 Berlin,
Daniel Rolles
James R. Macdonald Laboratory, Physics Department
Arnaud Rouzée
Max-Born-Institut, Max Born Straße 2A, Berlin 12489, Germany
Michael S. Schuurman
National Research Council Canada
Alcides Simao
Ruhr-Universität Bochum, Fakultät für Chemie und Biochemie, Organische Chemie II, Universitätsstraße 150 17 , 44801 Bochum,
Albert Stolow
Department of Chemistry and Biomolecular Sciences, University of Ottawa 1 , D’Iorio Hall, Ottawa, Ontario K1N 6N5,
Atia-Tul Noor
Deutsches Elektronen-Synchrotron DESY 1 , Notkestr. 85, 22607 Hamburg,
James Unwin
Claire Vallance
Tiffany Walmsley
Mark Brouard
Chemistry Research Laboratory, Department of Chemistry
Ruaridh Forbes
Linac Coherent Light Source