Extensive atomistic molecular dynamics simulations have been employed to study the structure and molecular orientational relaxation of azobenzene-based monolayers grafted to a solid substrate. Systems with surface coverage of 0.6 nm(2)/molecule were investigated over a wide temperature range ranging from 298 K, where the mesogens show local ordering and the monolayer dynamics was found to be glassy, up to 700 K, where the azobenzene groups have a nearly isotropic orientational distribution, with a subnanosecond characteristic orientational relaxation time scale. Biased simulations that model single-molecule thermal excitation and conformational isomerization have been conducted to obtain insight into the mechanisms for photoinduced athermal fluidization and monolayer reorganization observed experimentally in this system. Our simulations clearly indicate that trans-cis conformational isomerization transitions of azobenzene units can lead to reorientation of mesogens and to the formation of a monolayer with strong macroscopic in-plane nematic order. While local heating created by excitation process can facilitate this process, thermal excitation alone is not sufficient to induce ordering in the monolayer. Instead, the work done by a molecule undergoing cis-trans isomerization on the cage of neighboring molecules is the key mechanism for photofluidization and orientational ordering in dMR monolayers exposed to linearly polarized light leading to relaxation dynamics that can be described in terms of higher effective temperature. The obtained simulation results are discussed in light of recent experimental data reported for these systems.