Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Tracking the ultraviolet-induced photochemistry of thiophenone during and after ultrafast ring opening

Nature Chemistry volume 12, pages 795–800 (2020)Cite this article

Subjects

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.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Schematic of the UV excitation, ring opening and photoionization of thiophenone.
Fig. 2: Time-dependent photoelectron spectra of UV-excited thiophenone.
Fig. 3: Ab initio calculations of PESs and excited-state dynamics.
Fig. 4: Dynamics on the S0 PES following photoexcitation and non-radiative decay.

Similar content being viewed by others

Data availability

Data generated or analysed during this study are included in this Article (and its Supplementary Information). Source data are provided with this paper.

Code availability

The analysis codes used to generate the data presented in this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

References

  1. Minitti, M. P. et al. Imaging molecular motion: Femtosecond X-Ray scattering of the ring opening in 1,3-cyclohexadiene. Phys. Rev. Lett. 114, 255501 (2015).

    CAS  PubMed  Google Scholar 

  2. Pullen, M. G. et al. Imaging an aligned polyatomic molecule with laser-induced electron diffraction. Nat. Commun. 6, 7262 (2015).

    CAS  PubMed  PubMed Central  Google Scholar 

  3. Wolter, B. et al. Ultrafast electron diffraction imaging of bond breaking in di-ionized acetylene. Science 354, 308–312 (2016).

    CAS  PubMed  Google Scholar 

  4. Attar, A. R. et al. Femtosecond X-ray spectroscopy of an electrocyclic ring-opening reaction. Science 356, 54–59 (2017).

    CAS  PubMed  Google Scholar 

  5. Schuurman, M. S. & Stolow, A. Dynamics at conical intersections. Annu. Rev. Phys. Chem. 69, 427–450 (2018).

    CAS  PubMed  Google Scholar 

  6. Wolf, T. J. A. et al. The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction. Nat. Chem. 11, 504–509 (2019).

    CAS  PubMed  Google Scholar 

  7. Ruddock, J. M. et al. A deep UV trigger for ground-state ring-opening dynamics of 1,3-cyclohexadiene. Sci. Adv. 5, eaax6625 (2019).

    CAS  PubMed  PubMed Central  Google Scholar 

  8. Stankus, B. et al. Ultrafast X-ray scattering reveals vibrational coherence following Rydberg excitation. Nat. Chem. 11, 716–721 (2019).

    CAS  PubMed  Google Scholar 

  9. Browne, W. R. & Feringa, B. L. Light switching of molecules on surfaces. Annu. Rev. Phys. Chem. 60, 407–428 (2009).

    CAS  PubMed  Google Scholar 

  10. Kumpulainen, T., Lang, B., Rosspeintner, A. & Vauthey, E. Ultrafast elementary photochemical processes of organic molecules in liquid solution. Chem. Rev. 117, 10826–10939 (2017).

    CAS  PubMed  Google Scholar 

  11. Qi, J. et al. Light-driven transformable optical agent with adaptive functions for boosting cancer surgery outcomes. Nat. Commun. 9, 1848 (2018).

    PubMed  PubMed Central  Google Scholar 

  12. Deb, S. & Weber, P. M. The ultrafast pathway of photon-induced electrocyclic ring-opening reactions: The case of 1,3-cyclohexadiene. Annu. Rev. Phys. Chem. 62, 19–39 (2011).

    CAS  PubMed  Google Scholar 

  13. Arruda, B. C. & Sension, R. J. Ultrafast polyene dynamics: the ring opening of 1,3-cyclohexadiene derivatives. Phys. Chem. Chem. Phys. 16, 4439–4455 (2014).

    CAS  PubMed  Google Scholar 

  14. Petrović, V. S. et al. Transient X-ray fragmentation: Probing a prototypical photoinduced ring opening. Phys. Rev. Lett. 108, 253006 (2012).

    PubMed  Google Scholar 

  15. Rudakov, F. & Weber, P. M. Ground state recovery and molecular structure upon ultrafast transition through conical intersections in cyclic dienes. Chem. Phys. Lett. 470, 187–190 (2009).

    CAS  Google Scholar 

  16. Adachi, S., Sato, M. & Suzuki, T. Direct observation of ground-state product formation in a 1,3-cyclohexadiene ring-opening reaction. J. Phys. Chem. Lett. 6, 343–346 (2015).

    CAS  PubMed  Google Scholar 

  17. Breda, S., Reva, I. & Fausto, R. UV-induced unimolecular photochemistry of 2(5H)-furanone and 2(5H)-thiophenone isolated in low temperature inert matrices. Vib. Spectrosc. 50, 57–67 (2009).

    CAS  Google Scholar 

  18. Murdock, D. et al. Transient UV pump–IR probe investigation of heterocyclic ring-opening dynamics in the solution phase: the role played by nσ* states in the photoinduced reactions of thiophenone and furanone. Phys. Chem. Chem. Phys. 16, 21271–21279 (2014).

    CAS  PubMed  Google Scholar 

  19. Allaria, E. et al. Highly coherent and stable pulses from the FERMI seeded free-electron laser in the extreme ultraviolet. Nat. Photonics 6, 699–704 (2012).

    CAS  Google Scholar 

  20. Stolow, A., Bragg, A. E. & Neumark, D. M. Femtosecond time-resolved photoelectron spectroscopy. Chem. Rev. 104, 1719–1757 (2004).

    CAS  PubMed  Google Scholar 

  21. Suzuki, T. Time-resolved photoelectron spectroscopy of non-adiabatic electronic dynamics in gas and liquid phases. Int. Rev. Phys. Chem 31, 265–318 (2012).

    CAS  Google Scholar 

  22. Iikubo, R., Sekikawa, T., Harabuchi, Y. & Taketsugu, T. Structural dynamics of photochemical reactions probed by time-resolved photoelectron spectroscopy using high harmonic pulses. Faraday Discuss. 194, 147–160 (2016).

    CAS  PubMed  Google Scholar 

  23. Nishitani, J., West, C. W., Higashimura, C. & Suzuki, T. Time-resolved photoelectron spectroscopy of polyatomic molecules using 42-nm vacuum ultraviolet laser based on high harmonics generation. Chem. Phys. Lett. 684, 397–401 (2017).

    CAS  Google Scholar 

  24. Smith, A. D. et al. Mapping the complete reaction path of a complex photochemical reaction. Phys. Rev. Lett. 120, 183003 (2018).

    CAS  PubMed  Google Scholar 

  25. von Conta, A. et al. Conical-intersection dynamics and ground-state chemistry probed by extreme-ultraviolet time-resolved photoelectron spectroscopy. Nat. Commun. 9, 3162 (2018).

    Google Scholar 

  26. Squibb, R. J. et al. Acetylacetone photodynamics at a seeded free-electron laser. Nat. Commun. 9, 63 (2018).

    CAS  PubMed  PubMed Central  Google Scholar 

  27. Gorobtsov, O. Y. et al. Seeded X-ray free-electron laser generating radiation with laser statistical properties. Nat. Commun. 9, 4498 (2018).

    PubMed  PubMed Central  Google Scholar 

  28. Xie, B.-B. & Fang, W.-H. Combined quantum trajectory mean‐field and molecular mechanical (QTMF/MM) nonadiabatic dynamics simulations on the photoinduced ring‐opening reaction of 2(5H)‐thiophenone. ChemPhotoChem 3, 897–906 (2019).

    CAS  Google Scholar 

  29. Chin, W. S. et al. He I and He II photoelectron spectra of thiophenones. J. Electron Spectrosc. Relat. Phenomena 88-91, 97–101 (1998).

    CAS  Google Scholar 

  30. Tao, H. et al. Ultrafast internal conversion in ethylene. I. The excited state lifetime. J. Chem. Phys. 134, 244306 (2011).

    CAS  PubMed  Google Scholar 

  31. Mignolet, B., Curchod, B. F. E. & Martínez, T. J. Rich athermal ground-state chemistry triggered by dynamics through a conical intersection. Angew. Chem. Int. Ed. Engl. 55, 14993–14996 (2016).

    CAS  PubMed  Google Scholar 

  32. Bock, H., Mohmand, S., Hirabayashi, T. & Semkow, A. Gas-phase reactions. 29. Thioacrolein. J. Am. Chem. Soc. 104, 312–313 (1982).

    CAS  Google Scholar 

  33. Yang, C.-S., Bhattacharyya, S., Liu, L., Fang, W.-H. & Liu, K. Real-time tracking of the entangled pathways in the multichannel photodissociation of acetaldehyde. Chem. Sci. https://doi.org/10.1039/d0sc00063a (2020).

  34. Svetina, C. et al. The low density matter (LDM) beamline at FERMI: optical layout and first commissioning. J. Synchrotron Radiat. 22, 538–543 (2015).

    PubMed  PubMed Central  Google Scholar 

  35. Lyamayev, V. et al. A modular end-station for atomic, molecular, and cluster science at the low density matter beamline of FERMI@Elettra. J. Phys. B 46, 164007 (2013).

    Google Scholar 

  36. Finetti, P. et al. Pulse duration of seeded free-electron lasers. Phys. Rev. X 7, 021043 (2017).

    Google Scholar 

  37. Eland, J. H. D. et al. Complete two-electron spectra in double photoionization: the rare gases Ar, Kr, and Xe. Phys. Rev. Lett. 90, 053003 (2003).

    CAS  PubMed  Google Scholar 

  38. Zangrando, M. et al. Recent results of PADReS, the photon analysis delivery and reduction system, from the FERMI FEL commissioning and user operations. J. Synchrotron Radiat. 22, 565–570 (2015).

    CAS  PubMed  Google Scholar 

  39. Werner, H.-J. in Advances in Chemical Physics: Ab Initio Methods in Quantum Chemistry Part 2 Vol. 69 (ed. Lawley, K. P.) Ch. 1 (Wiley, 1987).

  40. Roos, B. O. in Advances in Chemical Physics: Ab Initio Methods in Quantum Chemistry Part 2 Vol. 69 (ed. Lawley, K. P.) Ch. 7 (Wiley, 1987).

  41. Hehre, W. J., Ditchfield, R. & Pople, J. A. Self-consistent molecular orbital methods. XII. Further extensions of Gaussian-type basis sets for use in molecular-orbital studies of organic-molecules. J. Chem. Phys. 56, 2257–2261 (1972).

    CAS  Google Scholar 

  42. Hariharan, P. C. & Pople, J. A. Influence of polarization functions on molecular-orbital hydrogenation energies. Theor. Chem. Acc. 28, 213–222 (1973).

    CAS  Google Scholar 

  43. Werner, H.-J. et al. MOLPRO, v.2012.1 (Molpro, 2012); https://www.molpro.net

  44. Hudock, H. R. et al. Ab initio molecular dynamics and time-resolved photoelectron spectroscopy of electronically excited uracil and thymine. J. Phys. Chem. A 111, 8500–8508 (2007).

    CAS  PubMed  Google Scholar 

  45. Shiozaki, T., Győrffyet, W., Celani, C. & Werner, H.-J. Communication: Extended multi-state complete active space second-order perturbation theory: Energy and nuclear gradients. J. Chem. Phys. 135, 081106 (2011).

    PubMed  Google Scholar 

  46. Granovsky, A. Extended multi-configuration quasi-degenerate perturbation theory: The new approach to multi-state multi-reference perturbation theory. J. Chem. Phys. 134, 214113 (2011).

    PubMed  Google Scholar 

  47. BAGEL Brilliantly Advanced General Electronic-Structure Library v.1.2.2 (Shiozaki Group, 2018); http://www.nubakery.org

  48. Ghigo, G., Roos, B. O. & Malmqvist, P. A. A modified definition of the zeroth-order Hamiltonian in multiconfigurational perturbation theory (CASPT2). Chem. Phys. Lett. 396, 142–149 (2004).

    CAS  Google Scholar 

  49. Tully, J. C. Molecular dynamics with electronic transitions. J. Chem. Phys. 93, 1061–1071 (1990).

    CAS  Google Scholar 

  50. Adamo, C. & Barone, V. Toward reliable density functional methods without adjustable parameters: The PBE0 model. J. Chem. Phys. 110, 6158–6169 (1999).

    CAS  Google Scholar 

  51. Ufimtsev, I. S. & Martínez, T. J. Quantum chemistry on graphical processing units. 3. analytical energy gradients, geometry optimization, and first principles molecular dynamics. J. Chem. Theory Comput. 5, 2619–2628 (2009).

    CAS  PubMed  Google Scholar 

Download references

Acknowledgements

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.

Author information

Author notes

  1. These authors contributed equally: Shashank Pathak, Lea M. Ibele.

Authors and Affiliations

  1. J.R. Macdonald Laboratory, Department of Physics, Kansas State University, Manhattan, KS, USA

    Shashank Pathak, Jan Tross & Daniel Rolles

  2. Department of Chemistry, Durham University, Durham, UK

    Lea M. Ibele & Basile F. E. Curchod

  3. European XFEL, Schenefeld, Germany

    Rebecca Boll

  4. Elettra-Sincrotrone Trieste S.C.p.A., Trieste, Italy

    Carlo Callegari, Alexander Demidovich, Michele Di Fraia, Luca Giannessi, Oksana Plekan & Kevin C. Prince

  5. Deutsches Elektronen-Synchrotron, Hamburg, Germany

    Benjamin Erk

  6. Department of Physics, University of Gothenburg, Gothenburg, Sweden

    Raimund Feifel & Richard J. Squibb

  7. Stanford PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Ruaridh Forbes

  8. Istituto Nazionale di Fisica Nucleare, Laboratori Nazionali di Frascati, Frascati, Italy

    Luca Giannessi

  9. School of Chemistry, University of New South Wales, Sydney, New South Wales, Australia

    Christopher S. Hansen

  10. Daresbury Laboratory, Warrington, UK

    David M. P. Holland

  11. Department of Chemistry, University College London, London, UK

    Rebecca A. Ingle

  12. Department of Chemistry, University of Oxford, Oxford, UK

    Robert Mason

  13. Centre for Translational Atomaterials, Swinburne University of Technology, Melbourne, Victoria, Australia

    Kevin C. Prince

  14. Max-Born-Institut, Berlin, Germany

    Arnaud Rouzée

  15. School of Chemistry, University of Bristol, Bristol, UK

    Michael N. R. Ashfold

Authors
  1. Shashank Pathak
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lea M. Ibele
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Rebecca Boll
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Carlo Callegari
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Alexander Demidovich
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Benjamin Erk
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Raimund Feifel
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Ruaridh Forbes
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Michele Di Fraia
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Luca Giannessi
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Christopher S. Hansen
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. David M. P. Holland
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Rebecca A. Ingle
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Robert Mason
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Oksana Plekan
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Kevin C. Prince
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Arnaud Rouzée
    View author publications

    You can also search for this author in PubMed Google Scholar

  18. Richard J. Squibb
    View author publications

    You can also search for this author in PubMed Google Scholar

  19. Jan Tross
    View author publications

    You can also search for this author in PubMed Google Scholar

  20. Michael N. R. Ashfold
    View author publications

    You can also search for this author in PubMed Google Scholar

  21. Basile F. E. Curchod
    View author publications

    You can also search for this author in PubMed Google Scholar

  22. Daniel Rolles
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

R.B., R.A.I., C.S.H., M.N.R.A. and D.R. conceived the experiment, the plans for which benefitted from further input from R. Forbes, D.M.P.H. and A.R. The experiment was conducted by S.P., R.A.I., R.B., C.C., A.D., B.E., R. Feifel, M.D.F., L.G., C.S.H., D.M.P.H., R.M., O.P., K.C.P., A.R., R.J.S., J.T., M.N.R.A. and D.R. at the FERMI free-electron laser facility. R. Feifel and R.J.S. provided and operated the magnetic bottle spectrometer. C.C., M.D.F. and O.P. prepared and operated the beamline and the low-density matter (LDM) instrument. A.D. and L.G. prepared and operated the optical laser and the free-electron laser, respectively. L.M.I. and B.F.E.C. performed the ab initio simulations, with contributions from R.A.I. Experimental data were analysed by S.P. and J.T. with contributions from C.C., R. Forbes, C.S.H., R.A.I., R.M. and A.R. Finally, S.P., L.M.I., R.B., R. Forbes, M.N.R.A., B.F.E.C. and D.R. interpreted the results and wrote the manuscript with input from all the authors.

Corresponding authors

Correspondence to Michael N. R. Ashfold, Basile F. E. Curchod or Daniel Rolles.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary discussion, Figs. 1–17 and Tables 1–3.

Source data

Source Data Fig. 2

Source data for Fig. 2.

Source Data Fig. 3

Source data for Fig. 3.

Source Data Fig. 4

Source data for Fig. 4.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Pathak, S., Ibele, L.M., Boll, R. et al. Tracking the ultraviolet-induced photochemistry of thiophenone during and after ultrafast ring opening. Nat. Chem. 12, 795–800 (2020). https://doi.org/10.1038/s41557-020-0507-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41557-020-0507-3

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing