Capturing electron-driven chiral dynamics in UV-excited molecules

Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review

Autoren

  • Vincent Wanie
  • Etienne Bloch
  • Erik P. Månsson
  • Lorenzo Colaizzi
  • Sergey Ryabchuk
  • Krishna Saraswathula
  • Andres F. Ordonez
  • David Ayuso
  • Olga Smirnova
  • Andrea Trabattoni
  • Valérie Blanchet
  • Nadia Ben Amor
  • Marie Catherine Heitz
  • Yann Mairesse
  • Bernard Pons
  • Francesca Calegari

Organisationseinheiten

Externe Organisationen

  • Deutsches Elektronen-Synchrotron (DESY)
  • Universite de Bordeaux
  • Universität Hamburg
  • Politecnico di Milano
  • Imperial College London
  • Queen Mary University of London
  • Max-Born-Institut für Nichtlineare Optik und Kurzzeitspektroskopie (MBI)
  • Technische Universität Berlin
  • Center for Free-Electron Laser Science (CFEL)
  • Centre national de la recherche scientifique (CNRS)
Forschungs-netzwerk anzeigen

Details

OriginalspracheEnglisch
Seiten (von - bis)109-115
Seitenumfang7
FachzeitschriftNATURE
Jahrgang630
Ausgabenummer8015
Frühes Online-Datum22 Mai 2024
PublikationsstatusVeröffentlicht - 6 Juni 2024

Abstract

Chiral molecules, used in applications such as enantioselective photocatalysis1, circularly polarized light detection2 and emission3 and molecular switches4,5, exist in two geometrical configurations that are non-superimposable mirror images of each other. These so-called (R) and (S) enantiomers exhibit different physical and chemical properties when interacting with other chiral entities. Attosecond technology might enable influence over such interactions, given that it can probe and even direct electron motion within molecules on the intrinsic electronic timescale6 and thereby control reactivity7–9. Electron currents in photoexcited chiral molecules have indeed been predicted to enable enantiosensitive molecular orientation10, but electron-driven chiral dynamics in neutral molecules have not yet been demonstrated owing to the lack of ultrashort, non-ionizing and perturbative light pulses. Here we use time-resolved photoelectron circular dichroism (TR-PECD)11–15 with an unprecedented temporal resolution of 2.9 fs to map the coherent electronic motion initiated by ultraviolet (UV) excitation of neutral chiral molecules. We find that electronic beatings between Rydberg states lead to periodic modulations of the chiroptical response on the few-femtosecond timescale, showing a sign inversion in less than 10 fs. Calculations validate this and also confirm that the combination of the photoinduced chiral current with a circularly polarized probe pulse realizes an enantioselective filter of molecular orientations following photoionization. We anticipate that our approach will enable further investigations of ultrafast electron dynamics in chiral systems and reveal a route towards enantiosensitive charge-directed reactivity.

ASJC Scopus Sachgebiete

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Capturing electron-driven chiral dynamics in UV-excited molecules. / Wanie, Vincent; Bloch, Etienne; Månsson, Erik P. et al.
in: NATURE, Jahrgang 630, Nr. 8015, 06.06.2024, S. 109-115.

Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review

Wanie, V, Bloch, E, Månsson, EP, Colaizzi, L, Ryabchuk, S, Saraswathula, K, Ordonez, AF, Ayuso, D, Smirnova, O, Trabattoni, A, Blanchet, V, Ben Amor, N, Heitz, MC, Mairesse, Y, Pons, B & Calegari, F 2024, 'Capturing electron-driven chiral dynamics in UV-excited molecules', NATURE, Jg. 630, Nr. 8015, S. 109-115. https://doi.org/10.48550/arXiv.2301.02002, https://doi.org/10.1038/s41586-024-07415-y, https://doi.org/10.1038/s41586-024-07676-7
Wanie, V., Bloch, E., Månsson, E. P., Colaizzi, L., Ryabchuk, S., Saraswathula, K., Ordonez, A. F., Ayuso, D., Smirnova, O., Trabattoni, A., Blanchet, V., Ben Amor, N., Heitz, M. C., Mairesse, Y., Pons, B., & Calegari, F. (2024). Capturing electron-driven chiral dynamics in UV-excited molecules. NATURE, 630(8015), 109-115. https://doi.org/10.48550/arXiv.2301.02002, https://doi.org/10.1038/s41586-024-07415-y, https://doi.org/10.1038/s41586-024-07676-7
Wanie V, Bloch E, Månsson EP, Colaizzi L, Ryabchuk S, Saraswathula K et al. Capturing electron-driven chiral dynamics in UV-excited molecules. NATURE. 2024 Jun 6;630(8015):109-115. Epub 2024 Mai 22. doi: 10.48550/arXiv.2301.02002, 10.1038/s41586-024-07415-y, 10.1038/s41586-024-07676-7
Wanie, Vincent ; Bloch, Etienne ; Månsson, Erik P. et al. / Capturing electron-driven chiral dynamics in UV-excited molecules. in: NATURE. 2024 ; Jahrgang 630, Nr. 8015. S. 109-115.
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title = "Capturing electron-driven chiral dynamics in UV-excited molecules",
abstract = "Chiral molecules, used in applications such as enantioselective photocatalysis1, circularly polarized light detection2 and emission3 and molecular switches4,5, exist in two geometrical configurations that are non-superimposable mirror images of each other. These so-called (R) and (S) enantiomers exhibit different physical and chemical properties when interacting with other chiral entities. Attosecond technology might enable influence over such interactions, given that it can probe and even direct electron motion within molecules on the intrinsic electronic timescale6 and thereby control reactivity7–9. Electron currents in photoexcited chiral molecules have indeed been predicted to enable enantiosensitive molecular orientation10, but electron-driven chiral dynamics in neutral molecules have not yet been demonstrated owing to the lack of ultrashort, non-ionizing and perturbative light pulses. Here we use time-resolved photoelectron circular dichroism (TR-PECD)11–15 with an unprecedented temporal resolution of 2.9 fs to map the coherent electronic motion initiated by ultraviolet (UV) excitation of neutral chiral molecules. We find that electronic beatings between Rydberg states lead to periodic modulations of the chiroptical response on the few-femtosecond timescale, showing a sign inversion in less than 10 fs. Calculations validate this and also confirm that the combination of the photoinduced chiral current with a circularly polarized probe pulse realizes an enantioselective filter of molecular orientations following photoionization. We anticipate that our approach will enable further investigations of ultrafast electron dynamics in chiral systems and reveal a route towards enantiosensitive charge-directed reactivity.",
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T1 - Capturing electron-driven chiral dynamics in UV-excited molecules

AU - Wanie, Vincent

AU - Bloch, Etienne

AU - Månsson, Erik P.

AU - Colaizzi, Lorenzo

AU - Ryabchuk, Sergey

AU - Saraswathula, Krishna

AU - Ordonez, Andres F.

AU - Ayuso, David

AU - Smirnova, Olga

AU - Trabattoni, Andrea

AU - Blanchet, Valérie

AU - Ben Amor, Nadia

AU - Heitz, Marie Catherine

AU - Mairesse, Yann

AU - Pons, Bernard

AU - Calegari, Francesca

N1 - Publisher Copyright: © The Author(s) 2024.

PY - 2024/6/6

Y1 - 2024/6/6

N2 - Chiral molecules, used in applications such as enantioselective photocatalysis1, circularly polarized light detection2 and emission3 and molecular switches4,5, exist in two geometrical configurations that are non-superimposable mirror images of each other. These so-called (R) and (S) enantiomers exhibit different physical and chemical properties when interacting with other chiral entities. Attosecond technology might enable influence over such interactions, given that it can probe and even direct electron motion within molecules on the intrinsic electronic timescale6 and thereby control reactivity7–9. Electron currents in photoexcited chiral molecules have indeed been predicted to enable enantiosensitive molecular orientation10, but electron-driven chiral dynamics in neutral molecules have not yet been demonstrated owing to the lack of ultrashort, non-ionizing and perturbative light pulses. Here we use time-resolved photoelectron circular dichroism (TR-PECD)11–15 with an unprecedented temporal resolution of 2.9 fs to map the coherent electronic motion initiated by ultraviolet (UV) excitation of neutral chiral molecules. We find that electronic beatings between Rydberg states lead to periodic modulations of the chiroptical response on the few-femtosecond timescale, showing a sign inversion in less than 10 fs. Calculations validate this and also confirm that the combination of the photoinduced chiral current with a circularly polarized probe pulse realizes an enantioselective filter of molecular orientations following photoionization. We anticipate that our approach will enable further investigations of ultrafast electron dynamics in chiral systems and reveal a route towards enantiosensitive charge-directed reactivity.

AB - Chiral molecules, used in applications such as enantioselective photocatalysis1, circularly polarized light detection2 and emission3 and molecular switches4,5, exist in two geometrical configurations that are non-superimposable mirror images of each other. These so-called (R) and (S) enantiomers exhibit different physical and chemical properties when interacting with other chiral entities. Attosecond technology might enable influence over such interactions, given that it can probe and even direct electron motion within molecules on the intrinsic electronic timescale6 and thereby control reactivity7–9. Electron currents in photoexcited chiral molecules have indeed been predicted to enable enantiosensitive molecular orientation10, but electron-driven chiral dynamics in neutral molecules have not yet been demonstrated owing to the lack of ultrashort, non-ionizing and perturbative light pulses. Here we use time-resolved photoelectron circular dichroism (TR-PECD)11–15 with an unprecedented temporal resolution of 2.9 fs to map the coherent electronic motion initiated by ultraviolet (UV) excitation of neutral chiral molecules. We find that electronic beatings between Rydberg states lead to periodic modulations of the chiroptical response on the few-femtosecond timescale, showing a sign inversion in less than 10 fs. Calculations validate this and also confirm that the combination of the photoinduced chiral current with a circularly polarized probe pulse realizes an enantioselective filter of molecular orientations following photoionization. We anticipate that our approach will enable further investigations of ultrafast electron dynamics in chiral systems and reveal a route towards enantiosensitive charge-directed reactivity.

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