I thought that BSSE referred to the error induced by the
*incompleteness in the basis set*, that is, the lack of a sufficient
number of basis functions, but I feel that what people are talking about
here is the error in the *overlap between wavefunctions* (or orbitals)

The name says it itself Basis Set SUPERPOSITION Error.
The description of the atom can be improved by using the basis of another atom (in a different place).

When you remove the second atom you noticeably affect the completeness of the basis, so the counterpoise correction (ghost atoms) is often used as a remedy for BSSE.

It does not however mean that with the second atom's basis your basis for atom1 became complete. No. It became better but still far from complete. The idea of BSSE (for calculation of binding energies) is at least NOT TO CHANGE the basis between two calculations, so that the error due to incompletness of the basis would cancel out.

Responder a