In this work, a computational model of state-to-state energy flow in gas ensembles is used to investigate collisional relaxation of excited OH, present as a minor species in various bath gases. Rovibrational quantum state populations are computed for each component species in ensembles consisting of 8000 molecules undergoing cycles of binary collisions. Results are presented as quantum state populations and as (approximate) modal temperatures for each species after each collision cycle. Equilibration of OH is slow with Ar as the partner but much faster when N(2) and/or O(2) forms the bath gas. This accelerated thermalization is shown to be the result of near-resonant vibration-vibration transfer, with vibrational deexcitation in OH matched in energy by excitation in bath molecules. Successive near-resonant events result in an energy cascade. Such processes are highly dependent on molecule pair and on initial OH vibrational state. OH rotational temperatures initially increase, but at equilibration, they are lower than those of other modes. Possible reasons for this observation in molecules such as OH are suggested. There are indications of an order of precedent in the equilibration process, with vibrations taking priority over rotations, and potential explanations for this phenomenon are discussed.