Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane

Borne KD, Cooper JC, Ashfold MNR, Bachmann J, Bhattacharyya S, Boll R, Bonanomi M, Bosch M, Callegari C, Centurion M, Coreno M, Curchod BFE, Danailov MB, Demidovich A, Di Fraia M, Erk B, Faccialà D, Feifel R, Forbes RJG, Hansen CS, Holland DMP, Ingle RA, Lindh R, Ma L, McGhee HG, Bhavya Muvva S, Figueira Nunes JP, Odate A, Pathak S, Plekan O, Prince KC, Rebernik P, Rouzée A, Rudenko A, Simoncig A, Squibb RJ, Venkatachalam AS, Vozzi C, Weber PM, Kirrander A, Rolles D (2024)

Publication Language: English

Publication Type: Journal article

Publication year: 2024

Journal

DOI: 10.1038/s41557-023-01420-w

Abstract

The light-induced ultrafast switching between molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Prior work observed signatures of ultrafast molecular dynamics in both isomers upon ultraviolet excitation but could not follow the electronic relaxation all the way back to the ground state experimentally. Here we study the electronic relaxation of quadricyclane after exciting in the ultraviolet (201 nanometres) using time-resolved gas-phase extreme ultraviolet photoelectron spectroscopy combined with non-adiabatic molecular dynamics simulations. We identify two competing pathways by which electronically excited quadricyclane molecules relax to the electronic ground state. The fast pathway (<100 femtoseconds) is distinguished by effective coupling to valence electronic states, while the slow pathway involves initial motions across Rydberg states and takes several hundred femtoseconds. Both pathways facilitate interconversion between the two isomers, albeit on different timescales, and we predict that the branching ratio of norbornadiene/quadricyclane products immediately after returning to the electronic ground state is approximately 3:2.

Authors with CRIS profile

Involved external institutions

Elettra Sincrotrone Trieste S.C.p.A. Italy (IT) University College London (UCL) United Kingdom (GB) Daresbury Laboratory United Kingdom (GB) Stanford National Accelerator Laboratory (SLAC) United States (USA) (US) University of Bristol United Kingdom (GB) Kansas State University United States (USA) (US) University of Nebraska-Lincoln United States (USA) (US) Istituto di Fotonica e Nanotecnologie (CNR-IFN) / Institute for photonics and nanotechnologies Italy (IT) Brown University United States (USA) (US) Politecnico di Milano Italy (IT) University of Oxford United Kingdom (GB) Max-Born-Institut für Nichtlineare Optik und Kurzzeitspektroskopie im Forschungsverbund Berlin e.V. / Max Born Institute for Nonlinear Optics and Short Pulse Spectroscopy Germany (DE) University of Gothenburg / Göteborgs universitet Sweden (SE) Deutsches Elektronen-Synchrotron DESY Germany (DE) European XFEL GmbH Germany (DE) University of New South Wales (UNSW) Australia (AU) Uppsala University Sweden (SE)

How to cite

APA:

Borne, K.D., Cooper, J.C., Ashfold, M.N.R., Bachmann, J., Bhattacharyya, S., Boll, R.,... Rolles, D. (2024). Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane. Nature Chemistry. https://dx.doi.org/10.1038/s41557-023-01420-w

MLA:

Borne, Kurtis D., et al. "Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane." Nature Chemistry (2024).

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