Dispersion-controlled excited-state dynamics in azobenzene photoisomerization

Weak interactions, like London dispersion forces, are cumulative in nature and have been thought to be essential for only the structure and stability of large molecular systems. Only recently has their relevance for chemical reactivity been recognized. Until today, their role in photoreactions and s...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Hauptverfasser: Saßmannshausen, Torben (VerfasserIn) , Oberhof, Nils (VerfasserIn) , Strauss, Marcel A. (VerfasserIn) , Slavov, Chavdar (VerfasserIn) , Wegner, Hermann A. (VerfasserIn) , Dreuw, Andreas (VerfasserIn) , Wachtveitl, Josef (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: Decembrie 30, 2025
In: Journal of the American Chemical Society
Year: 2026, Jahrgang: 148, Heft: 1, Pages: 997-1003
ISSN:1520-5126
DOI:10.1021/jacs.5c16915
Online-Zugang:Verlag, kostenfrei, Volltext: https://doi.org/10.1021/jacs.5c16915
Verlag, kostenfrei, Volltext: https://pubs.acs.org/doi/10.1021/jacs.5c16915
Volltext
Verfasserangaben:Torben Sassmannshausen, Nils Oberhof, Marcel A. Strauss, Chavdar Slavov, Hermann A. Wegner, Andreas Dreuw, and Josef Wachtveitl
Beschreibung
Zusammenfassung:Weak interactions, like London dispersion forces, are cumulative in nature and have been thought to be essential for only the structure and stability of large molecular systems. Only recently has their relevance for chemical reactivity been recognized. Until today, their role in photoreactions and subsequent ultrafast excited-state processes has remained elusive. Here, we show the impact of London dispersion on the excited-state behavior and the outcome of the photoreaction of the iconic photoswitch azobenzene as a representative example. Increased dispersion interactions between substituents decisively prolong the excited-state lifetimes by preventing direct passage through the conical intersection. This significantly alters the dynamics of the Z to E photoisomerization. We expect our findings to lead to increased research interest in such “dispersion-controlled excited-state dynamics” relevant for the steering of ultrafast processes.
Beschreibung:Gesehen am 19.03.2026
Beschreibung:Online Resource
ISSN:1520-5126
DOI:10.1021/jacs.5c16915