The photoisomerization mechanism of azobenzene: a semiclassical simulation of nonadiabatic dynamics.

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-->pi* and pi-->pi* excitations and both cis-->trans and trans-->cis conversions have been considered. We show that in all cases the torsion around the N==N 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.

Cite this paper

@article{Ciminelli2004ThePM, title={The photoisomerization mechanism of azobenzene: a semiclassical simulation of nonadiabatic dynamics.}, author={Cosimo Ciminelli and Giovanni Granucci and Maurizio Persico}, journal={Chemistry}, year={2004}, volume={10 9}, pages={2327-41} }