A new definition is suggested for basis set superposition error, Other sources of basis set incompleteness error in the interaction energy are considered. Comparison is made with the counterpoise correction. An explanation is provided for the tendency in water and HF dimers for the counterpoise-corr
The magnitude of intramolecular basis set superposition error
β Scribed by Frank Jensen
- Publisher
- Elsevier Science
- Year
- 1996
- Tongue
- English
- Weight
- 303 KB
- Volume
- 261
- Category
- Article
- ISSN
- 0009-2614
No coin nor oath required. For personal study only.
β¦ Synopsis
It is shown that part of what normally is considered a basis set effect on relative energies, more properly may be interpreted as intramolecular basis set superposition error.
π SIMILAR VOLUMES
Possible generalizations of the Boys-Bernardi counterpoise correction scheme to the case of relaxed monomer geometries is discussed. It is emphasized that the monomer relaxation energy should be calculated in the basis of free monomers, because it becomes ambiguous in the supermolecule basis.
Basis set superposition error (BSSE) is computed for the H-bonded system (F-H...F)-by the Boys-Bernardi counterpoise scheme using a wide array of basis sets at both the SCF and MP2 levels. Although the BSSE can be fairly large for the complexation process, it is comparable in magnitude for the endpo
Basis-set superposition corrections to properties of tightly bound systems have been studied. The effects are demonstrated for two different properties: the dissociation energy ofN, and the geometrical conformation of C,. The definition of these corrections is somewhat ambiguous, since the constitue
A model is formulated which avoids the basis set superposition error (BSSE) problem at the correlation level. A projector is constructed which removes the BSSE when applied to a wavefunction. This projection can simply be included as an additional step in a usual configuration interaction method. Te
A thorough investlgatlon ot the proper scheme to correct for basis set superpositlon errors is performed for the He dimer withm the CEPA(1) method. The BSSE proves. even for this small system, extremely difficult to avoid, and it is m no way negligible. Through comparison wth perturbation-theory est