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.show moreshow less

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Metadaten
Author:Jan Boyke Schönborn, Bernd Hartke
DOI:https://doi.org/10.1039/c3cp53495b
ISSN:1463-9076 (print)
ISSN:1463-9084 (online)
Pubmed Id:http://www.ncbi.nlm.nih.gov/pubmed?term=24358466
Parent Title (English):Physical chemistry, chemical physics : a journal of European Chemical Societies
Publisher:Royal Society of Chemistry
Place of publication:Cambridge
Document Type:Article
Language:English
Year of first Publication:2014
Year of Completion:2014
Release Date:2017/03/27
Volume:16
Issue:6
Pagenumber:8
First Page:2483
Last Page:2490
Funder:German Science Foundation DFG via the Collaborative Research Center [SFB677]
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer Review:Referiert