Tracking the Ultraviolet Photochemistry of Thiophenone During and After the Initial Ultrafast Ring Opening

Shashank Pathak; Lea M. Ibele; Rebecca Boll; Carlo Callegari; Alexander Demidovich; Benjamin Erk; Raimund Feifel; Ruaridh Forbes; Michele Di Fraia; Luca Giannessi; Christopher S. Hansen; David M.P. Holland; Rebecca A. Ingle; Robert Mason; Oksana Plekan; Kevin C. Prince; Arnaud Rouzée; Richard J. Squibb; Jan Tross; Michael N.R. Ashfold; Basile F.E. Curchod; Daniel Rolles

doi:10.1038/s41557-020-0507-3

Tracking the Ultraviolet Photochemistry of Thiophenone During and After the Initial Ultrafast Ring Opening

Shashank Pathak, Lea M. Ibele, Rebecca Boll, Carlo Callegari, Alexander Demidovich, Benjamin Erk, Raimund Feifel, Ruaridh Forbes, Michele Di Fraia, Luca Giannessi, Christopher S. Hansen, David M.P. Holland, Rebecca A. Ingle, Robert Mason, Oksana Plekan, Kevin C. Prince, Arnaud Rouzée, Richard J. Squibb, Jan Tross, Michael N.R. Ashfold^*Basile F.E. Curchod^*, Daniel Rolles^*

^*Corresponding author for this work

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Abstract

Photoinduced isomerization reactions lie at the heart of many chemical processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics occurring on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. Here we apply time-resolved photoelectron spectroscopy with a seeded extreme ultraviolet free-electron laser to trace the ultrafast ring opening of gas-phase thiophenone molecules following ultraviolet photoexcitation. When combined with ab initio electronic structure and molecular dynamics calculations of the excited- and ground-state molecules, the results provide insights into both the electronic and nuclear dynamics of this fundamental class of reactions. The initial ring opening and non-adiabatic coupling to the electronic ground state are shown to be driven by ballistic S–C bond extension and to be complete within 350 fs. Theory and experiment also enable visualization of the rich ground-state dynamics that involve the formation of, and interconversion between, ring-opened isomers and the cyclic structure, as well as fragmentation over much longer timescales.

Original language	English
Pages (from-to)	795-800
Number of pages	6
Journal	Nature Chemistry
Volume	12
Issue number	9
DOIs	https://doi.org/10.1038/s41557-020-0507-3
Publication status	Published - 20 Jul 2020

Bibliographical note

Funding Information:
S.P., J.T. and D.R. were supported by the National Science Foundation (NSF) grant PHYS-1753324. S.P. was also partially supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy (DOE) under grant no. DE-FG02-86ER13491. Travel to FERMI for S.P., D.M.P.H., R.M., J.T. and D.R. was supported by LaserLab Europe. This work made use of the facilities of the Hamilton HPC Service of Durham University. M.N.R.A., C.S.H. and R.A.I. acknowledge the Engineering and Physical Sciences Research Council (EPSRC) for funding (EP/L005913/1), while L.M.I. acknowledges the EPSRC for a doctoral studentship (EP/R513039/1). C.S.H. also acknowledges funding from the Australian Research Council (ARC, DE200100549). M.N.R.A. thanks W.-H. Fang (Beijing Normal University) for permission to share data28 prior to its publication. B.F.E.C. acknowledges funding from the European Union Horizon 2020 research and innovation programme under grant agreement no. 803718 (SINDAM). D.M.P.H. was supported by the Science and Technology Facilities Council, UK. R.F. and R.J.S. acknowledge financial support from the Swedish Research Council, the Knut and Alice Wallenberg Foundation, Sweden, and the Faculty of Natural Science of the University of Gothenburg. We thank the technical and scientific teams at FERMI for their hospitality and their support during the beamtime. We also acknowledge helpful discussions with A. Rudenko during the preparation of the beamtime proposal and during the data interpretation and with S. Bhattacharyya during the data analysis and interpretation.

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© 2020, The Author(s), under exclusive licence to Springer Nature Limited.

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Pathak, S., Ibele, L. M., Boll, R., Callegari, C., Demidovich, A., Erk, B., Feifel, R., Forbes, R., Di Fraia, M., Giannessi, L., Hansen, C. S., Holland, D. M. P., Ingle, R. A., Mason, R., Plekan, O., Prince, K. C., Rouzée, A., Squibb, R. J., Tross, J., ... Rolles, D. (2020). Tracking the Ultraviolet Photochemistry of Thiophenone During and After the Initial Ultrafast Ring Opening. Nature Chemistry, 12(9), 795-800. https://doi.org/10.1038/s41557-020-0507-3

@article{0dbf64a5c11b4c5fb43a5cb36bea9ca0,

title = "Tracking the Ultraviolet Photochemistry of Thiophenone During and After the Initial Ultrafast Ring Opening",

abstract = "Photoinduced isomerization reactions lie at the heart of many chemical processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics occurring on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. Here we apply time-resolved photoelectron spectroscopy with a seeded extreme ultraviolet free-electron laser to trace the ultrafast ring opening of gas-phase thiophenone molecules following ultraviolet photoexcitation. When combined with ab initio electronic structure and molecular dynamics calculations of the excited- and ground-state molecules, the results provide insights into both the electronic and nuclear dynamics of this fundamental class of reactions. The initial ring opening and non-adiabatic coupling to the electronic ground state are shown to be driven by ballistic S–C bond extension and to be complete within 350 fs. Theory and experiment also enable visualization of the rich ground-state dynamics that involve the formation of, and interconversion between, ring-opened isomers and the cyclic structure, as well as fragmentation over much longer timescales.",

author = "Shashank Pathak and Ibele, {Lea M.} and Rebecca Boll and Carlo Callegari and Alexander Demidovich and Benjamin Erk and Raimund Feifel and Ruaridh Forbes and {Di Fraia}, Michele and Luca Giannessi and Hansen, {Christopher S.} and Holland, {David M.P.} and Ingle, {Rebecca A.} and Robert Mason and Oksana Plekan and Prince, {Kevin C.} and Arnaud Rouz{\'e}e and Squibb, {Richard J.} and Jan Tross and Ashfold, {Michael N.R.} and Curchod, {Basile F.E.} and Daniel Rolles",

note = "Funding Information: S.P., J.T. and D.R. were supported by the National Science Foundation (NSF) grant PHYS-1753324. S.P. was also partially supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy (DOE) under grant no. DE-FG02-86ER13491. Travel to FERMI for S.P., D.M.P.H., R.M., J.T. and D.R. was supported by LaserLab Europe. This work made use of the facilities of the Hamilton HPC Service of Durham University. M.N.R.A., C.S.H. and R.A.I. acknowledge the Engineering and Physical Sciences Research Council (EPSRC) for funding (EP/L005913/1), while L.M.I. acknowledges the EPSRC for a doctoral studentship (EP/R513039/1). C.S.H. also acknowledges funding from the Australian Research Council (ARC, DE200100549). M.N.R.A. thanks W.-H. Fang (Beijing Normal University) for permission to share data28 prior to its publication. B.F.E.C. acknowledges funding from the European Union Horizon 2020 research and innovation programme under grant agreement no. 803718 (SINDAM). D.M.P.H. was supported by the Science and Technology Facilities Council, UK. R.F. and R.J.S. acknowledge financial support from the Swedish Research Council, the Knut and Alice Wallenberg Foundation, Sweden, and the Faculty of Natural Science of the University of Gothenburg. We thank the technical and scientific teams at FERMI for their hospitality and their support during the beamtime. We also acknowledge helpful discussions with A. Rudenko during the preparation of the beamtime proposal and during the data interpretation and with S. Bhattacharyya during the data analysis and interpretation. Publisher Copyright: {\textcopyright} 2020, The Author(s), under exclusive licence to Springer Nature Limited.",

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month = jul,

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doi = "10.1038/s41557-020-0507-3",

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Pathak, S, Ibele, LM, Boll, R, Callegari, C, Demidovich, A, Erk, B, Feifel, R, Forbes, R, Di Fraia, M, Giannessi, L, Hansen, CS, Holland, DMP, Ingle, RA, Mason, R, Plekan, O, Prince, KC, Rouzée, A, Squibb, RJ, Tross, J, Ashfold, MNR , Curchod, BFE & Rolles, D 2020, 'Tracking the Ultraviolet Photochemistry of Thiophenone During and After the Initial Ultrafast Ring Opening', Nature Chemistry, vol. 12, no. 9, pp. 795-800. https://doi.org/10.1038/s41557-020-0507-3

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T1 - Tracking the Ultraviolet Photochemistry of Thiophenone During and After the Initial Ultrafast Ring Opening

AU - Pathak, Shashank

AU - Ibele, Lea M.

AU - Boll, Rebecca

AU - Callegari, Carlo

AU - Demidovich, Alexander

AU - Erk, Benjamin

AU - Feifel, Raimund

AU - Forbes, Ruaridh

AU - Di Fraia, Michele

AU - Giannessi, Luca

AU - Hansen, Christopher S.

AU - Holland, David M.P.

AU - Ingle, Rebecca A.

AU - Mason, Robert

AU - Plekan, Oksana

AU - Prince, Kevin C.

AU - Rouzée, Arnaud

AU - Squibb, Richard J.

AU - Tross, Jan

AU - Ashfold, Michael N.R.

AU - Curchod, Basile F.E.

AU - Rolles, Daniel

N1 - Funding Information: S.P., J.T. and D.R. were supported by the National Science Foundation (NSF) grant PHYS-1753324. S.P. was also partially supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Department of Energy (DOE) under grant no. DE-FG02-86ER13491. Travel to FERMI for S.P., D.M.P.H., R.M., J.T. and D.R. was supported by LaserLab Europe. This work made use of the facilities of the Hamilton HPC Service of Durham University. M.N.R.A., C.S.H. and R.A.I. acknowledge the Engineering and Physical Sciences Research Council (EPSRC) for funding (EP/L005913/1), while L.M.I. acknowledges the EPSRC for a doctoral studentship (EP/R513039/1). C.S.H. also acknowledges funding from the Australian Research Council (ARC, DE200100549). M.N.R.A. thanks W.-H. Fang (Beijing Normal University) for permission to share data28 prior to its publication. B.F.E.C. acknowledges funding from the European Union Horizon 2020 research and innovation programme under grant agreement no. 803718 (SINDAM). D.M.P.H. was supported by the Science and Technology Facilities Council, UK. R.F. and R.J.S. acknowledge financial support from the Swedish Research Council, the Knut and Alice Wallenberg Foundation, Sweden, and the Faculty of Natural Science of the University of Gothenburg. We thank the technical and scientific teams at FERMI for their hospitality and their support during the beamtime. We also acknowledge helpful discussions with A. Rudenko during the preparation of the beamtime proposal and during the data interpretation and with S. Bhattacharyya during the data analysis and interpretation. Publisher Copyright: © 2020, The Author(s), under exclusive licence to Springer Nature Limited.

PY - 2020/7/20

Y1 - 2020/7/20

N2 - Photoinduced isomerization reactions lie at the heart of many chemical processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics occurring on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. Here we apply time-resolved photoelectron spectroscopy with a seeded extreme ultraviolet free-electron laser to trace the ultrafast ring opening of gas-phase thiophenone molecules following ultraviolet photoexcitation. When combined with ab initio electronic structure and molecular dynamics calculations of the excited- and ground-state molecules, the results provide insights into both the electronic and nuclear dynamics of this fundamental class of reactions. The initial ring opening and non-adiabatic coupling to the electronic ground state are shown to be driven by ballistic S–C bond extension and to be complete within 350 fs. Theory and experiment also enable visualization of the rich ground-state dynamics that involve the formation of, and interconversion between, ring-opened isomers and the cyclic structure, as well as fragmentation over much longer timescales.

AB - Photoinduced isomerization reactions lie at the heart of many chemical processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics occurring on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. Here we apply time-resolved photoelectron spectroscopy with a seeded extreme ultraviolet free-electron laser to trace the ultrafast ring opening of gas-phase thiophenone molecules following ultraviolet photoexcitation. When combined with ab initio electronic structure and molecular dynamics calculations of the excited- and ground-state molecules, the results provide insights into both the electronic and nuclear dynamics of this fundamental class of reactions. The initial ring opening and non-adiabatic coupling to the electronic ground state are shown to be driven by ballistic S–C bond extension and to be complete within 350 fs. Theory and experiment also enable visualization of the rich ground-state dynamics that involve the formation of, and interconversion between, ring-opened isomers and the cyclic structure, as well as fragmentation over much longer timescales.

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JO - Nature Chemistry

JF - Nature Chemistry

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Tracking the Ultraviolet Photochemistry of Thiophenone During and After the Initial Ultrafast Ring Opening

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Tracking the Ultraviolet Photochemistry of Thiophenone During and After the Initial Ultrafast Ring Opening

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