Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane

Borne, Kurtis D.; Cooper, Joseph C.; Ashfold, Michael N. R.; Bachmann, Julien; Bhattacharyya, Surjendu; Boll, Rebecca; Bonanomi, Matteo; Bosch, Michael; Callegari, Carlo; Centurion, Martin; Coreno, Marcello; Curchod, Basile F. E.; Danailov, Miltcho B.; Demidovich, Alexander; Di Fraia, Michele; Erk, Benjamin; Faccialà, Davide; Feifel, Raimund; Forbes, Ruaridh J. G.; Hansen, Christopher S.; Holland, David M. P.; Ingle, Rebecca A.; Lindh, Roland; Ma, Lingyu; McGhee, Henry G.; Muvva, Sri Bhavya; Nunes, Joao Pedro Figueira; Odate, Asami; Pathak, Shashank; Plekan, Oksana; Prince, Kevin C.; Rebernik, Primoz; Rouzée, Arnaud; Rudenko, Artem; Simoncig, Alberto; Squibb, Richard J.; Venkatachalam, Anbu Selvam; Vozzi, Caterina; Weber, Peter M.; Kirrander, Adam; Rolles, Daniel

doi:10.1038/s41557-023-01420-w

Title: Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane

Journal Article · Fri Feb 02 00:00:00 UTC 2024 · Nature Chemistry

DOI: https://doi.org/10.1038/s41557-023-01420-w · OSTI ID:2283778

Borne, Kurtis D.; Cooper, Joseph C.;

;

; Bhattacharyya, Surjendu;

; Bonanomi, Matteo;

;

; Coreno, Marcello;

; Danailov, Miltcho B.;

;

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.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: Australian Research Council; Engineering and Physical Sciences Research Council (EPSRC); Knut and Alice Wallenberg Foundation; National Science Foundation (NSF); Swedish Research Council; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-76SF00515; FG02-86ER13491; SC0020276

OSTI ID:: 2283778

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 4 Vol. 16; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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