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 p->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.
|Autori interni:||GRANUCCI, GIOVANNI|
|Autori:||C. CIMINELLI; GRANUCCI G; M. PERSICO|
|Titolo:||The photoisomerization mechanism of azobenzene: a semiclassical simulation of nonadiabatic dynamics|
|Anno del prodotto:||2004|
|Digital Object Identifier (DOI):||10.1002/chem.200305415|
|Appare nelle tipologie:||1.1 Articolo in rivista|