The most comprehensive nucleofugality scale, based on the correlation and solvolytic rate constants of benzhydrylium derivatives, has recently been proposed by Mayr and co-workers (Acc. Chem. Res., 2010, 43, 1537-1549). In this work, the possibility of employing quantum chemical calculations in further determination of nucleofugality (Nf) parameters of leaving groups is explored. Whereas the heterolytic transition state of benzhydryl carboxylate cannot be optimized by quantum chemical calculations, the possibility of an alternative model reaction is examined in order to obtain nucleofugality parameters of various aliphatic carboxylates, which can properly be included in the current nucleofugality scale. For that purpose, ground and transition state structures have been optimized for the proposed model reaction, which includes anchimerically assisted heterolytic dissociation of cis-2,3-dihydroxycyclopropyl trans-carboxylates. The validity of the model reaction as well as of applied DFT methods in the presence of the IEFPCM solvation model is verified by correlating calculated free energies of activation of the model reaction with literature experimental data for solvolysis of reference dianisylmethyl carboxylates. For this purpose the ability of several functionals (including popular B3LYP) is examined, among which the M06-2X gives the best results. The very good correlation indicates acceptable accurate relative reactivities of aliphatic carboxylates, and enables the estimation of rate constants for solvolysis of other dianisylmethyl carboxylates in aqueous ethanol mixtures, from which the corresponding Nf parameters are determined using mentioned Mayr's equation. In addition, DFT calculations confirm the previous experimental observation that the abilities of aliphatic carboxylate leaving groups in solution are governed by the inductive effect of substituents attached to the carboxyl group.