Azobenzenes can serve as model compounds for the study of trans-cis isomerization in more complex molecules. We have performed time-resolved spectroscopy in solutions containing free azobenzene chromophores and diols with a view to obtaining the energy levels and lifetimes of the excited states. A transition route based on experimental results for the theoretically calculated energy level scheme is proposed. Physical observations of surface relief in thin films of azobenzene polymers when irradiated with polarized light are reported. These include two beam polarization holographic observations and single beam transmission measurements through a mask, followed by atomic force microscope and profiler investigations. It is concluded that none of the prevalent theories can explain all the observed facts.