Monitoring the evolution of relative product populations at early times during a photochemical reaction

Joao P.F. Nunes; Lea-Maria Ibele; Shashank Pathak; Andrew R. Attar; Surjendu Bhattacharyya; Rebecca Boll; Kurtis D Borne; Martin Centurion; Benjamin Erk; Ming-Fu Lin; Ruaridh J G Forbes; Nathan Goff; Christopher S Hansen; Matthias Hoffmann; David M P Holland; Rebecca A Ingle; Duan Luo; Sri Bhavya Muvva; Alex Reid; Arnaud Rouzee; Artem Rudenko; Sajib K  Saha; Xiao Z Shen; Anbu S Venkatachalam; Xi J Wang; Matt R Ware; Stephen P. Weathersby; Kyle Wilkin; Thomas J A Wolf; Yan W Xiong; Jie Yang; Michael N R Ashfold; Daniel Rolles; Basile F E Curchod

doi:10.1021/jacs.3c13046

Monitoring the evolution of relative product populations at early times during a photochemical reaction

Joao P.F. Nunes, Lea-Maria Ibele, Shashank Pathak, Andrew R. Attar, Surjendu Bhattacharyya, Rebecca Boll, Kurtis D Borne, Martin Centurion, Benjamin Erk, Ming-Fu Lin, Ruaridh J G Forbes, Nathan Goff, Christopher S Hansen, Matthias Hoffmann, David M P Holland, Rebecca A Ingle, Duan Luo, Sri Bhavya Muvva, Alex Reid, Arnaud RouzeeArtem Rudenko, Sajib K Saha, Xiao Z Shen, Anbu S Venkatachalam, Xi J Wang, Matt R Ware, Stephen P. Weathersby, Kyle Wilkin, Thomas J A Wolf, Yan W Xiong, Jie Yang, Michael N R Ashfold^*, Daniel Rolles^*, Basile F E Curchod^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

18 Citations (Scopus)

Abstract

Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps toward understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species among the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5H)-thiophenone. This strategy provides experimental validation of the predicted high (∼50%) yield of an episulfide isomer containing a strained three-membered ring within ∼1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.

Original language	English
Pages (from-to)	4134–4143
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	146
Issue number	6
Early online date	6 Feb 2024
DOIs	https://doi.org/10.1021/jacs.3c13046
Publication status	Published - 14 Feb 2024

Bibliographical note

Funding Information:
The SLAC MeV-UED facility is operated as part of the Linac Coherent Light Source at the SLAC National Accelerator Laboratory, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. Other authors are funded through National Science Foundation grant PHYS1753324 (AV, DR); Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (M.R.W., T.J.A.W.), under grant nos. DE-FG02-86ER13491 (S.P., A.R.), DE-SC0019451 (K.B.), DE-SC0020276 (S.B.), DE-SC0017995 (N.G.), and DE-SC0020276 (J.P.F.N., S.K.S., M.C.); Engineering and Physical Sciences Research Council grant nos. EP/L005913/1 (M.N.R.A.), EP/V026690/1 (B.F.E.C.), EP/X026973/1 (B.F.E.C.), and EP/R513039/1 (L.M.I.); ANR Q-DeLight project, Grant No. ANR-20-CE29-0014 of the French Agence Nationale de la Recherche (L.M.I.); Australian Research Council grant no. DE200100549 (C.S.H.); European Union Horizon 2020 research and innovation program grant no. 803718 (B.F.E.C.); and Science and Technology Facilities Council (D.M.P.H.).

Publisher Copyright:
© 2024 The Authors.

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Physical & Theoretical

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2 Finished
2 Active

OAFI - Basile Curchod - EPSRC Programme Grant - UCL lead: A Universal Approach to Using Quantum Dynamics for Real World Problems: Applying Coherent States for MolecularDynamics Simulations (COSMOS)
Curchod, B. F. E. (Principal Investigator)
1/10/23 → 30/09/29
Project: Research
Ultrafast Photochemical Dynamics in Complex Environments
Orr-Ewing, A. J. (Principal Investigator), Oliver, T. (Principal Investigator) & Curchod, B. F. E. (Principal Investigator)
1/09/21 → 31/08/27
Project: Research
SINDAM: 8084 - SINDAM - ERC 803718 - Basile Curchod
Curchod, B. F. E. (Principal Investigator)
1/03/22 → 31/12/24
Project: Research

Cite this

Nunes, J. P. F., Ibele, L.-M., Pathak, S., Attar, A. R., Bhattacharyya, S., Boll, R., Borne, K. D., Centurion, M., Erk, B., Lin, M.-F., Forbes, R. J. G., Goff, N., Hansen, C. S., Hoffmann, M., Holland, D. M. P., Ingle, R. A., Luo, D., Muvva, S. B., Reid, A., ... Curchod, B. F. E. (2024). Monitoring the evolution of relative product populations at early times during a photochemical reaction. Journal of the American Chemical Society, 146(6), 4134–4143. https://doi.org/10.1021/jacs.3c13046

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title = "Monitoring the evolution of relative product populations at early times during a photochemical reaction",

abstract = "Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps toward understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species among the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5H)-thiophenone. This strategy provides experimental validation of the predicted high (∼50\%) yield of an episulfide isomer containing a strained three-membered ring within ∼1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.",

author = "Nunes, \{Joao P.F.\} and Lea-Maria Ibele and Shashank Pathak and Attar, \{Andrew R.\} and Surjendu Bhattacharyya and Rebecca Boll and Borne, \{Kurtis D\} and Martin Centurion and Benjamin Erk and Ming-Fu Lin and Forbes, \{Ruaridh J G\} and Nathan Goff and Hansen, \{Christopher S\} and Matthias Hoffmann and Holland, \{David M P\} and Ingle, \{Rebecca A\} and Duan Luo and Muvva, \{Sri Bhavya\} and Alex Reid and Arnaud Rouzee and Artem Rudenko and Saha, \{Sajib K\} and Shen, \{Xiao Z\} and Venkatachalam, \{Anbu S\} and Wang, \{Xi J\} and Ware, \{Matt R\} and Weathersby, \{Stephen P.\} and Kyle Wilkin and Wolf, \{Thomas J A\} and Xiong, \{Yan W\} and Jie Yang and Ashfold, \{Michael N R\} and Daniel Rolles and Curchod, \{Basile F E\}",

note = "Funding Information: The SLAC MeV-UED facility is operated as part of the Linac Coherent Light Source at the SLAC National Accelerator Laboratory, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. Other authors are funded through National Science Foundation grant PHYS1753324 (AV, DR); Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (M.R.W., T.J.A.W.), under grant nos. DE-FG02-86ER13491 (S.P., A.R.), DE-SC0019451 (K.B.), DE-SC0020276 (S.B.), DE-SC0017995 (N.G.), and DE-SC0020276 (J.P.F.N., S.K.S., M.C.); Engineering and Physical Sciences Research Council grant nos. EP/L005913/1 (M.N.R.A.), EP/V026690/1 (B.F.E.C.), EP/X026973/1 (B.F.E.C.), and EP/R513039/1 (L.M.I.); ANR Q-DeLight project, Grant No. ANR-20-CE29-0014 of the French Agence Nationale de la Recherche (L.M.I.); Australian Research Council grant no. DE200100549 (C.S.H.); European Union Horizon 2020 research and innovation program grant no. 803718 (B.F.E.C.); and Science and Technology Facilities Council (D.M.P.H.). Publisher Copyright: {\textcopyright} 2024 The Authors.",

year = "2024",

month = feb,

day = "14",

doi = "10.1021/jacs.3c13046",

language = "English",

volume = "146",

pages = "4134–4143",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

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Nunes, JPF, Ibele, L-M, Pathak, S, Attar, AR, Bhattacharyya, S, Boll, R, Borne, KD, Centurion, M, Erk, B, Lin, M-F, Forbes, RJG, Goff, N, Hansen, CS, Hoffmann, M, Holland, DMP, Ingle, RA, Luo, D, Muvva, SB, Reid, A, Rouzee, A, Rudenko, A, Saha, SK, Shen, XZ, Venkatachalam, AS, Wang, XJ, Ware, MR, Weathersby, SP, Wilkin, K, Wolf, TJA, Xiong, YW, Yang, J, Ashfold, MNR, Rolles, D & Curchod, BFE 2024, 'Monitoring the evolution of relative product populations at early times during a photochemical reaction', Journal of the American Chemical Society, vol. 146, no. 6, pp. 4134–4143. https://doi.org/10.1021/jacs.3c13046

TY - JOUR

T1 - Monitoring the evolution of relative product populations at early times during a photochemical reaction

AU - Nunes, Joao P.F.

AU - Ibele, Lea-Maria

AU - Pathak, Shashank

AU - Attar, Andrew R.

AU - Bhattacharyya, Surjendu

AU - Boll, Rebecca

AU - Borne, Kurtis D

AU - Centurion, Martin

AU - Erk, Benjamin

AU - Lin, Ming-Fu

AU - Forbes, Ruaridh J G

AU - Goff, Nathan

AU - Hansen, Christopher S

AU - Hoffmann, Matthias

AU - Holland, David M P

AU - Ingle, Rebecca A

AU - Luo, Duan

AU - Muvva, Sri Bhavya

AU - Reid, Alex

AU - Rouzee, Arnaud

AU - Rudenko, Artem

AU - Saha, Sajib K

AU - Shen, Xiao Z

AU - Venkatachalam, Anbu S

AU - Wang, Xi J

AU - Ware, Matt R

AU - Weathersby, Stephen P.

AU - Wilkin, Kyle

AU - Wolf, Thomas J A

AU - Xiong, Yan W

AU - Yang, Jie

AU - Ashfold, Michael N R

AU - Rolles, Daniel

AU - Curchod, Basile F E

N1 - Funding Information: The SLAC MeV-UED facility is operated as part of the Linac Coherent Light Source at the SLAC National Accelerator Laboratory, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. Other authors are funded through National Science Foundation grant PHYS1753324 (AV, DR); Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (M.R.W., T.J.A.W.), under grant nos. DE-FG02-86ER13491 (S.P., A.R.), DE-SC0019451 (K.B.), DE-SC0020276 (S.B.), DE-SC0017995 (N.G.), and DE-SC0020276 (J.P.F.N., S.K.S., M.C.); Engineering and Physical Sciences Research Council grant nos. EP/L005913/1 (M.N.R.A.), EP/V026690/1 (B.F.E.C.), EP/X026973/1 (B.F.E.C.), and EP/R513039/1 (L.M.I.); ANR Q-DeLight project, Grant No. ANR-20-CE29-0014 of the French Agence Nationale de la Recherche (L.M.I.); Australian Research Council grant no. DE200100549 (C.S.H.); European Union Horizon 2020 research and innovation program grant no. 803718 (B.F.E.C.); and Science and Technology Facilities Council (D.M.P.H.). Publisher Copyright: © 2024 The Authors.

PY - 2024/2/14

Y1 - 2024/2/14

N2 - Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps toward understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species among the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5H)-thiophenone. This strategy provides experimental validation of the predicted high (∼50%) yield of an episulfide isomer containing a strained three-membered ring within ∼1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.

AB - Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps toward understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species among the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5H)-thiophenone. This strategy provides experimental validation of the predicted high (∼50%) yield of an episulfide isomer containing a strained three-membered ring within ∼1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.

U2 - 10.1021/jacs.3c13046

DO - 10.1021/jacs.3c13046

M3 - Article (Academic Journal)

C2 - 38317439

SN - 0002-7863

VL - 146

SP - 4134

EP - 4143

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 6

ER -

Monitoring the evolution of relative product populations at early times during a photochemical reaction

Abstract

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OAFI - Basile Curchod - EPSRC Programme Grant - UCL lead: A Universal Approach to Using Quantum Dynamics for Real World Problems: Applying Coherent States for MolecularDynamics Simulations (COSMOS)

Ultrafast Photochemical Dynamics in Complex Environments

SINDAM: 8084 - SINDAM - ERC 803718 - Basile Curchod

Cite this