Photochemical dynamics of E-methylfurylfulgide
- 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 |
---|---|
URN: | urn:nbn:de:kobv:517-opus4-94516 |
Untertitel (Englisch): | kinematic effects on photorelaxation dynamics of furylfulgides |
Schriftenreihe (Bandnummer): | Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe (237) |
Publikationstyp: | Postprint |
Sprache: | Englisch |
Datum der Erstveröffentlichung: | 28.11.2013 |
Erscheinungsjahr: | 2013 |
Veröffentlichende Institution: | Universität Potsdam |
Datum der Freischaltung: | 11.08.2016 |
Freies Schlagwort / Tag: | decay dynamics; fulgides; implementation; molecular-dynamics; photoinduced nonadiabatic dynamics; photoisomerization; ring-closure; semiempirical methods; spectroscopy; state |
Erste Seite: | 2483 |
Letzte Seite: | 2490 |
Quelle: | Phys. Chem. Chem. Phys. (2014) Nr. 16, S. 2483-2490. - DOI: 10.1039/C3CP53495B |
Organisationseinheiten: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
DDC-Klassifikation: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Peer Review: | Referiert |
Publikationsweg: | Open Access |
Lizenz (Deutsch): | Keine öffentliche Lizenz: Unter Urheberrechtsschutz |