The effects of dynamics, surface temperature, and tunneling on the dissociative chemisorption of hydrogen on Cu(111) are explored using a dynamically biased precursor-mediated microcanonical trapping (d-PMMT) model. Transition state vibrational frequencies were taken from recent generalized gradient approximation density functional theory (GGA-DFT) electronic structure calculations, and the model’s few remaining parameters were fixed by optimizing simulations to a limited number of quantum-state-resolved associative desorption experiments. The d-PMMT model reproduces a diverse variety of dissociative chemisorption and associative desorption experimental results and, importantly, largely captures the surface temperature dependence of quantum-state-resolved dissociative sticking coefficients. Molecular translational energy parallel to the surface was treated as a spectator degree of freedom. The efficacy of molecular rotational energy to promote dissociation, relative to normal translational energy, varied ...