The Photoisomerization Mechanism of Azobenzene: A Semiclassical Simulation of Nonadiabatic Dynamics
- 21 April 2004
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 10 (9) , 2327-2341
- https://doi.org/10.1002/chem.200305415
Abstract
We have simulated the photoisomerization dynamics of azobenzene, taking into account internal conversion and geometrical relaxation processes, by means of a semiclassical surface hopping approach. Both n→π* and π→π* excitations and both cis→trans and trans→cis conversions have been considered. We show that in all cases the torsion around the NN double bond is the preferred mechanism. The quantum yields measured are correctly reproduced and the observed differences are explained as a result of the competition between the inertia of the torsional motion and the premature deactivation of the excited state. Recent time-resolved spectroscopic experiments are interpreted in the light of the simulated dynamics.Keywords
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