Cavity shape effect on pKa prediction of small amines

Cavity shape affects the free energy of solvation by which pK(a) changes. In this work. we have used different level of theories and basis sets combine with the PCM model of solvation to predict acidity constants of small ammonium ions during their protonation in aqueous solution. Three different kinds of models including UAHF, Bondi, and Pauling have been chosen to study that how a cavity shape changes acidity constant. Contrary to the previous results of literature for bulky ammonium ions, the difference between our results is not very much. Predictions show that in some levels and basis sets UAHF model is the best, while in some other cases it is the worst. (C) 2009 Elsevier B.V. All rights reserved.