An analytical consideration is made for the simplest possible model in which the BSSE problem may appear. The results demonstrate that BSSE cannot be corrected in any consistent manner by readjusting the monomer energies to the enlarged basis, because the energy effects caused by BSSE and by the true interactions are not additive. The way out is to correct BSSE, or prevent its appearance by an appropriate analysis and special treatment at the supermolecule level, permitting to keep the supermolecule problem consistent with the monomer calculations, as provided by the "chemical Hamiltonian" approach recently introduced.
- BSSE, non-additivity of
- BSSE, preventing appearance of
- Basis set superposition error (BSSE)
- Intermolecular interactions
- Super-molecule calculations
ASJC Scopus subject areas