Excited state dynamics with the direct trajectory surface hopping method: azobenzene and its derivatives as a case study

We review the recent studies of the photoisomerization dynamics of azobenzene and its derivatives by surface hopping simulations, based on semiempirical potential energy surfaces. We examine the ability of semiclassical methods to predict the excited state dynamics and to reproduce transient spectroscopic signals, that constitute the most direct experimental evidence in this field. We show that the available simulation methods yield a deep insight in the mechanism of photochemical reactions and excited state decay, and a fairly good quantitative agreement with experimental findings. Probably the most important technical improvements we can envisage concern the surface hopping algorithm and the usage of ab initio data in the simulation of transient spectra. Concerning azobenzene, our results show that the isomerization mechanism is torsion of the N=N double bond, both by n -> pi* and by pi -> pi* excitation. The influence of the solvent and the findings of some recent femtochemistry experiments deserve further work to be fully interpreted