Transparent alumina is often processed with sintering additives such as, Y, La, and Mg, in order to limit its grain growth at high sintering temperatures. Usually, these additives segregate to the grain boundaries due to their larger cationic size than Al and low solubility in bulk alpha-alumina. The grain boundary excess of these additives plays a key role in determining stable grain boundary complexions and thereby, the grain growth characteristics of the polycrystalline alumina. In the current work, the grain boundary segregation of trivalent (Y, La) as well as bivalent (Mg) dopants on several alumina grain boundaries was simulated using the force field based energy minimization method. Calculated segregation energy plots and atomistic structure analysis, for the case of trivalent dopants, suggest that there is a critical concentration (3-4 atoms/nm(2)) for achieving the lowest mobility monolayer grain boundary complexion. The bivalent dopant Mg plays a role in grain boundary complexion through creating ordered arrays of oxygen vacancies at the grain boundary and helps create the space for the easier occupation of the grain boundary cationic sites by the trivalent dopants in case of codoping. It was also observed that the twin grain boundaries are more preferable in comparison to general high angle grain boundaries to obtain mono layer complexions, which are necessary for limiting grain growth. The use of atomistic simulations can thus guide the experimentalist towards optimum dopant concentrations to better control ceramic microstructures. In a more general sense the possibility of second phase formation or an incipient second phase for high grain boundary concentrations >8 cations/nm(2) is briefly discussed. (C) 2016 Elsevier Ltd. All rights reserved.