We performed computational simulations of the photodynamics of a self-assembled monolayer (SAM) of an azobenzene derivative (azobiphenyl, ABPT) on a gold surface. An excitonic approach was adopted in a semiempirical framework, which allowed us to consider explicitly the electronic degrees of freedom of 12 azobenzene chromophores. The surface hopping scheme was used for nonadiabatic molecular dynamics simulations. According to our results for an all trans-ABPT SAM, the excitation energy transfer between different chromophores, very fast in the ππ∗ manifold, does not occur between nπ∗ states. As a consequence, the excitation transfer does not play an important role in the quenching of the azobenzene photoisomerization in the SAM (experimentally observed and reproduced by our calculations) which, instead, has to be attributed to steric effects.