Correlation balance in basis sets for electronic structure calculations

The balanced addition of polarization functions to the 6–31G and 6–311G basis sets for correlated wave functions is evaluated using bond energy predictions at the MP2 and full MP4 levels as a measure of correlation‐balanced basis sets. The homolytic dissociations of the XH bonds in H₂, CH₄, NH₃, H₂O, and HF and the XY bonds in C₂H₆, NH₂NH₂, HOOH, and CH₃OH are used as the basis for the evaluation. It is found that correlation balance is achieved for HH, XH, and XY bonds, particularly at the MP2 level, only if at least as many polarization sets, and sometimes more, are added to the hydrogens as are added to the heavy atoms.