Using the new parameters for PM3/SMD †, PM6/SMD † and DFTB/SMD †, we compare the obtained RMSE with other approaches to obtain solvent free energies such as HF/6-31G(d)/SMD (one of the levels of theory used in the original SMD parameterization), PM3/COSMO and PM6/COSMO for the MNSOL data set (Table and Figure ). The overall accuracy of PM3/SMD † is now similar to HF/SMD, although the RMSE value is 0.4 and 0.6 kcal/mol higher for neutral molecules and cations, while the RMSE is 0.7 kcal/mol lower for anions. For PM6 the overall RMSE is 1.4 kcal/mol higher than HF, and the RMSE for neutral molecules is 2.3 kcal/mol higher. On the other hand, the RMSE for cations is only 0.1 kcal/mol higher, while the RMSE for anions is 0.8 kcal/mol lower compared to HF. Finally, for DFTB the overall RMSE value (4.1 kcal/mol) is in between those for PM3 and PM6 as is the RMSE values for neutral molecules (3.9 kcal/mol). But for cations the RMSE (3.7 kcal/mol) is significantly lower than the other methods while the RMSE for anions (5.1 kcal/mol) is very similar.