Photochemical dynamics of E-methylfurylfulgide-kinematic effects on photorelaxation dynamics of furylfulgides
- With the present theoretical study of the photochemical switching of E-methylfurylfulgide we contribute an important step towards the understanding of the photochemical processes in furylfulgide-related molecules. We have carried out large-scale, full-dimensional direct semiempirical configuration-interaction surface-hopping dynamics of the photoinduced ring-closure reaction. Simulated static and dynamical UV/Vis-spectra show good agreement with experimental data of the same molecule. By a careful investigation of our dynamical data, we were able to identify marked differences to the dynamics of the previously studied E-isopropylfurylfulgide. With our simulations we can not only reproduce the experimentally observed quantum yield differences qualitatively but we can also pinpoint two reasons for them: kinematics and pre-orientation. With our analysis, we thus offer straightforward molecular explanations for the high sensitivity of the photodynamics towards seemingly minor changes in molecular constitution. Beyond the realm ofWith the present theoretical study of the photochemical switching of E-methylfurylfulgide we contribute an important step towards the understanding of the photochemical processes in furylfulgide-related molecules. We have carried out large-scale, full-dimensional direct semiempirical configuration-interaction surface-hopping dynamics of the photoinduced ring-closure reaction. Simulated static and dynamical UV/Vis-spectra show good agreement with experimental data of the same molecule. By a careful investigation of our dynamical data, we were able to identify marked differences to the dynamics of the previously studied E-isopropylfurylfulgide. With our simulations we can not only reproduce the experimentally observed quantum yield differences qualitatively but we can also pinpoint two reasons for them: kinematics and pre-orientation. With our analysis, we thus offer straightforward molecular explanations for the high sensitivity of the photodynamics towards seemingly minor changes in molecular constitution. Beyond the realm of furylfulgides, these insights provide additional guidance to the rational design of photochemically switchable molecules.…
Verfasserangaben: | Jan Boyke Schönborn, Bernd Hartke |
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DOI: | https://doi.org/10.1039/c3cp53495b |
ISSN: | 1463-9076 |
ISSN: | 1463-9084 |
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/24358466 |
Titel des übergeordneten Werks (Englisch): | Physical chemistry, chemical physics : a journal of European Chemical Societies |
Verlag: | Royal Society of Chemistry |
Verlagsort: | Cambridge |
Publikationstyp: | Wissenschaftlicher Artikel |
Sprache: | Englisch |
Jahr der Erstveröffentlichung: | 2014 |
Erscheinungsjahr: | 2014 |
Datum der Freischaltung: | 27.03.2017 |
Band: | 16 |
Ausgabe: | 6 |
Seitenanzahl: | 8 |
Erste Seite: | 2483 |
Letzte Seite: | 2490 |
Fördernde Institution: | German Science Foundation DFG via the Collaborative Research Center [SFB677] |
Organisationseinheiten: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer Review: | Referiert |