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Time-Resolved X‑ray Photoelectron Spectroscopy: Ultrafast Dynamics in CS2 Probed at the S 2p Edge

Time-Resolved X‑ray Photoelectron Spectroscopy: Ultrafast Dynamics in CS2 Probed at the S 2p Edge
Time-Resolved X‑ray Photoelectron Spectroscopy: Ultrafast Dynamics in CS2 Probed at the S 2p Edge
Recent developments in X-ray free-electron lasers have enabled a novel site-selective probe of coupled nuclear and electronic dynamics in photoexcited molecules, time-resolved X-ray photoelectron spectroscopy (TRXPS). We present results from a joint experimental and theoretical TRXPS study of the well-characterized ultraviolet photodissociation of CS2, a prototypical system for understanding non-adiabatic dynamics. These results demonstrate that the sulfur 2p binding energy is sensitive to changes in the nuclear structure following photoexcitation, which ultimately leads to dissociation into CS and S photoproducts. We are able to assign the main X-ray spectroscopic features to the CS and S products via comparison to a first-principles determination of the TRXPS based on ab initio multiple-spawning simulations. Our results demonstrate the use of TRXPS as a local probe of complex ultrafast photodissociation dynamics involving multimodal vibrational coupling, nonradiative transitions between electronic states, and multiple final product channels.
1948-7185
7126-7133
Gabalski, Ian
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Allum, Felix
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Seidu, Issaka
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Britton, Mathew
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Brenner, Gunter
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Bromberger, Hubertus
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Brouard, Mark
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Bucksbaum, Philip H.
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Burt, Michael
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Cryan, James P.
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Driver, Taran
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Ekanayake, Nagitha
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Erk, Benjamin
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Garg, Diksha
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Gougoula, Eva
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Heathcote, David
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Hockett, Paul
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Holland, David M.P.
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Howard, Andrew J.
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Kumar, Sonu
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Lee, Jason W.L.
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Li, Siqi
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McManus, Joseph
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Mikosch, Jochen
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Milesevic, Dennis
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Minns, Russell
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Neville, Simon P.
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et al.,
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Gabalski, Ian
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Allum, Felix
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Seidu, Issaka
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Britton, Mathew
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Brenner, Gunter
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Bromberger, Hubertus
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Brouard, Mark
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Bucksbaum, Philip H.
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Burt, Michael
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Cryan, James P.
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Driver, Taran
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Ekanayake, Nagitha
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Erk, Benjamin
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Garg, Diksha
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Gougoula, Eva
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Heathcote, David
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Hockett, Paul
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Holland, David M.P.
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Howard, Andrew J.
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Kumar, Sonu
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Lee, Jason W.L.
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Li, Siqi
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McManus, Joseph
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Mikosch, Jochen
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Milesevic, Dennis
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Minns, Russell
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Neville, Simon P.
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et al.,
96c90377-641f-4276-9d09-6968e3f36258

Gabalski, Ian, Allum, Felix, Seidu, Issaka, Britton, Mathew, Brenner, Gunter, Bromberger, Hubertus, Brouard, Mark, Bucksbaum, Philip H., Burt, Michael, Cryan, James P., Driver, Taran, Ekanayake, Nagitha, Erk, Benjamin, Garg, Diksha, Gougoula, Eva, Heathcote, David, Hockett, Paul, Holland, David M.P., Howard, Andrew J., Kumar, Sonu, Lee, Jason W.L., Li, Siqi, McManus, Joseph, Mikosch, Jochen, Milesevic, Dennis, Minns, Russell, Neville, Simon P. and et al., (2023) Time-Resolved X‑ray Photoelectron Spectroscopy: Ultrafast Dynamics in CS2 Probed at the S 2p Edge. The Journal of Physical Chemistry Letters, 14 (31), 7126-7133. (doi:10.1021/acs.jpclett.3c01447).

Record type: Article

Abstract

Recent developments in X-ray free-electron lasers have enabled a novel site-selective probe of coupled nuclear and electronic dynamics in photoexcited molecules, time-resolved X-ray photoelectron spectroscopy (TRXPS). We present results from a joint experimental and theoretical TRXPS study of the well-characterized ultraviolet photodissociation of CS2, a prototypical system for understanding non-adiabatic dynamics. These results demonstrate that the sulfur 2p binding energy is sensitive to changes in the nuclear structure following photoexcitation, which ultimately leads to dissociation into CS and S photoproducts. We are able to assign the main X-ray spectroscopic features to the CS and S products via comparison to a first-principles determination of the TRXPS based on ab initio multiple-spawning simulations. Our results demonstrate the use of TRXPS as a local probe of complex ultrafast photodissociation dynamics involving multimodal vibrational coupling, nonradiative transitions between electronic states, and multiple final product channels.

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Accepted/In Press date: 2023
Published date: 10 August 2023
Additional Information: Funding Information: The authors acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at FLASH. Beamtime was allocated for Proposal F-20200773. The research was further supported by the CALIPSOplus project under Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. This research was supported in part through the Maxwell computational resources operated at Deutsches Elektronen-Synchrotron DESY (Hamburg, Germany). The authors gratefully acknowledge the work of the scientific and technical teams at FLASH. The authors acknowledge the Max Planck Society for funding the development and the initial operation of the CAMP end-station within the Max Planck Advanced Study Group at CFEL and for providing this equipment for CAMP@FLASH. The installation of CAMP@FLASH was partially funded by BMBF Grants 05K10KT2, 05K13KT2, 05K16KT3, and 05K10KTB from FSP-302. R.F. and F.A. gratefully acknowledge support from the Linac Coherent Light Source, SLAC National Accelerator Laboratory, which is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-76SF00515. J.P.C. and P.H.B. are supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (BES), Chemical Sciences, Geosciences, and Biosciences Division, AMOS Program. D.R. is supported by National Science Foundation (NSF) Grant PHYS-1753324 and is thankful to LCLS and the Stanford PULSE Institute for their hospitality and financial support during a sabbatical. I.G. was supported by a NDSEG Fellowship. A. Stolow thanks the NRC-uOttawa Joint Centre for Extreme Photonics (JCEP) for financial support. A. Stolow and M.S.S. thank the NSERC Discovery Grants program and NRC CSTIP Quantum Sensors Project QSP-075-1 for financial support. J.U., T.W., and M. Burt are grateful for support from the UK EPSRC (EP/S028617/1). A CC-BY license is applied to the author-accepted manuscript arising from this submission, in accordance with UKRI open access conditions. J.U. is also grateful to the States of Jersey for studentship funding. T.W. additionally thanks the UK EPSRC and Jesus College, Oxford, for studentship funding. J.W.L.L. acknowledges financial support from the Helmholtz-ERC Recognition Award (ERC-RA-0043) of the Helmholtz Association (HGF). W.O.R. thanks the University of Southampton and the STFC XFEL hub for physical sciences for a Ph.D. studentship. R.S.M. gratefully acknowledges financial support from the EPSRC (EP/R010609/1) and the Leverhulme Trust (RPG-2021-257). C.V., D.H., and M. Brouard acknowledge support from EPSRC Programme Grants EP/V026690/1 and EP/T021675/1. D.M.P.H. is grateful to the Science and Technology Facilities Council (United Kingdom) for financial support. J. Mikosch gratefully acknowledges funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme within a Consolidator Grant (CoG Agreement 101003142). Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.

Identifiers

Local EPrints ID: 481136
URI: http://eprints.soton.ac.uk/id/eprint/481136
ISSN: 1948-7185
PURE UUID: 24cd7605-059c-47ac-b532-d7405650afac
ORCID for Russell Minns: ORCID iD orcid.org/0000-0001-6775-2977

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Date deposited: 16 Aug 2023 16:41
Last modified: 18 Mar 2024 03:20

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Contributors

Author: Ian Gabalski
Author: Felix Allum
Author: Issaka Seidu
Author: Mathew Britton
Author: Gunter Brenner
Author: Hubertus Bromberger
Author: Mark Brouard
Author: Philip H. Bucksbaum
Author: Michael Burt
Author: James P. Cryan
Author: Taran Driver
Author: Nagitha Ekanayake
Author: Benjamin Erk
Author: Diksha Garg
Author: Eva Gougoula
Author: David Heathcote
Author: Paul Hockett
Author: David M.P. Holland
Author: Andrew J. Howard
Author: Sonu Kumar
Author: Jason W.L. Lee
Author: Siqi Li
Author: Joseph McManus
Author: Jochen Mikosch
Author: Dennis Milesevic
Author: Russell Minns ORCID iD
Author: Simon P. Neville
Author: et al.

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