TY  - JOUR
AU  - Borne, Kurtis D.
AU  - Cooper, Joseph C.
AU  - ashfold, michael
AU  - Bachmann, Julien
AU  - Bhattacharyya, Surjendu
AU  - Boll, Rebecca
AU  - Bonanomi, Matteo
AU  - Bosch, Michael
AU  - Callegari, Carlo
AU  - Centurion, Martin
AU  - Coreno, Marcello
AU  - Curchod, Basile
AU  - Danailov, Miltcho B.
AU  - Demidovich, Alexander
AU  - Di Fraia, Michele
AU  - Erk, Benjamin
AU  - Facciala, Davide
AU  - Feifel, Raimund
AU  - Forbes, Ruaridh
AU  - Hansen, Christopher
AU  - Holland, David
AU  - Ingle, Rebecca
AU  - Lindh, Roland
AU  - Ma, Lingyu
AU  - McGhee, Henry G.
AU  - Muvva, Sri Bhavya
AU  - Nunes, Joao Pedro Figueira
AU  - Odate, Asami
AU  - Pathak, Shashank
AU  - Plekan, Oksana
AU  - Prince, Kevin
AU  - Rebernik, Primoz
AU  - Rouzée, Arnaud
AU  - Rudenko, Artem
AU  - Simoncig, Alberto
AU  - Squibb, Richard
AU  - Venkatachalam, Anbu
AU  - Vozzi, Caterina
AU  - Weber, Peter M.
AU  - Kirrander, Adam
AU  - Rolles, Daniel
TI  - Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane
JO  - Nature chemistry
VL  - 16
IS  - 4
SN  - 1755-4330
CY  - London
PB  - Nature Publishing Group
M1  - PUBDB-2024-01444
SP  - 499-505
PY  - 2024
AB  - 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. 
LB  - PUB:(DE-HGF)16
C6  - pmid:38307994
UR  - <Go to ISI:>//WOS:001156518100001
DO  - DOI:10.1038/s41557-023-01420-w
UR  - https://bib-pubdb1.desy.de/record/605377
ER  -