Investigation of G4(MP2)-XK theory for antimony compounds' thermochemistry.

The heats of formation of thirty-five molecules containing antimony atoms have been calculated using G4(MP2)-XK, B3LYP, M06, M06-HF, M06-2X, BMK, wB97XD, and TPSSh atomization. The discrepancies between the predicted and the reported heats of formation vary in the range of 0.0-83 kcal mol-1 when compared with experimental and literature. The best agreement with experimental and literature data was achieved by using G4(MP2)-XK. The functionals used did not show results as good as G4(MP2)-XK. In its development, G4 (MP2)-XK showed itself comparable in accuracy to the G4(MP2)-6X. Importantly, the precision of G4(MP2)-XK for heavier elements such as antimony is similar to that of the first- and second-row species, although it contains parameters that are only adjusted to the systems of the first two rows. In this study, we can observe that G4(MP2)-XK has excellent requirements for elements such as antimony and leads us to believe that its scope will be further expanded in future studies with formation enthalpy such as iodine and xenonium.

Assessment of pKa Determination for Monocarboxylic Acids with an Accurate Theoretical Composite Method: G4CEP.

For 22 monoprotic acids, pKa values were calculated using the G4CEP composite theory. The solvation effect was included considering the continuous SMD solvation model; SMD and one explicit water molecule; and SMD, one water molecule, and linear correction with respect to the experimental pKa values. The three tests provided mean absolute errors equal to 0.83, 0.51, and 0.30 pKa units, respectively, indicating excellent performance of the G4CEP method. Comparison with density functional theory at the B3LYP and BMK levels showed that these results are quickly obtained but with a significant error. The best performance of the functionals was obtained from the combination of SMD, one explicit water molecule, linear regression correction, and basis set including diffuse functions. However, the dispersion of the results with DFT can lead to deviations of up to two pKa units, whereas for G4CEP the largest deviations seldom exceed one pKa unit.