Unusual photochemical dynamics of a bridged azobenzene derivative.
In a large-scale simulation study of ultrafast photochemical dynamics for an azobenzene compound with an additional ethylenic bridge we have found unexpected features: while the dynamics starting from the Z isomer follow a barrierless path with steep gradients, the dynamics starting from the E isomer proceed through a different conical intersection surrounded by a rather flat potential energy landscape and then encounter a sizeable barrier in the electronic ground state that markedly influences the reaction behavior. Direct comparisons with experimental static UV spectra, quantum yields, and transient absorption spectra show good agreement and reveal signatures of this unusual behavior.
Carstensen
Ole
O
Institut für Physikalische Chemie, Christian-Albrechts-Universität, Olshausenstraße 40, D-24098 Kiel, Germany.
Sielk
Jan
J
Schönborn
Jan Boyke
JB
Granucci
Giovanni
G
Hartke
Bernd
B