The basis set superposition error in multilevel methods: a test on the H2O and HF dimer

The basis set superposition error (BSSE) is often very important in the accurate calculation of dimerization energies. Accurate prediction of thermochemical properties requires appropriate consideration of the basis set incompleteness error. Multilevel methods introduce adjustable parameters to reproduce experimental data, that is, the higher level correction (HLC) in G3 and adjustable coefficients in the MCCM. However, the HLC term is cancelled out and the adjustable coefficients in the MCCM do not remove the BSSE completely. We have calculated the BSSE involved in the multilevel methods. The H₂O and HF dimer systems were used as a test case. This study shows that empirical coefficients do reduce the BSSE in some cases and an MCCM with good parameters can be used to reproduce dimerization energies within chemical accuracy without the BSSE correction.