𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Perturbation analysis of the supermolecule interaction energy and the basis set superposition error

✍ Scribed by Sławomir M. Cybulski; Grzegorz Chałasiński

Publisher
Elsevier Science
Year
1992
Tongue
English
Weight
766 KB
Volume
197
Category
Article
ISSN
0009-2614

No coin nor oath required. For personal study only.

✦ Synopsis

The supermolecule interaction energies at the self-consistent field and the second-order Moller-Plesset perturbation theory levels are analyzed using the polarization approximation perturbation theory of intermolecular interactions. The results for the He-H+ complex show that the perturbation expansion converges and its sum is identical with the supermolecule interaction energy. The counterpoise-corrected supermolecule interaction energies for various complexes in the region of small intermolecular overlap are in excellent agreement with the perturbation results for both the basis sets of monomers and the basis set of the entire complex. Comparison of the results obtained with large and small basis sets for the He-H+ and He-Li+ complexes is used to emphasize the need to remove the basis set superposition error and to demonstrate the correctness of the counterpoise procedure.

📜 SIMILAR VOLUMES

Comparison of basis set superposition er
Comparison of basis set superposition error corrected perturbation theories for calculating intermolecular interaction energies
✍ G. J. Halász; Á. Vibók; I. Mayer 📂 Article 📅 1999 🏛 John Wiley and Sons 🌐 English ⚖ 281 KB 👁 2 views

Recently, two different but conceptually similar basis set Ž . superposition error BSSE free second-order perturbation theoretical schemes were developed by us that are being based on the chemical Hamiltonian Ž . approach CHA . Using these CHA-MP2 and CHA-PT2 methods, a comparison is made between th

The magnitude of intramolecular basis se
The magnitude of intramolecular basis set superposition error
✍ Frank Jensen 📂 Article 📅 1996 🏛 Elsevier Science 🌐 English ⚖ 303 KB

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.

Monomer geometry relaxation and the basi
Monomer geometry relaxation and the basis set superposition error
✍ I. Mayer; P.R. Surján 📂 Article 📅 1992 🏛 Elsevier Science 🌐 English ⚖ 161 KB

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.

The effect of basis set superposition er
The effect of basis set superposition error on the convergence of intermolecular interaction energies for deprotonated complexes
✍ Masao Masamura 📂 Article 📅 2004 🏛 John Wiley and Sons 🌐 English ⚖ 96 KB

## Abstract The intermolecular interaction energies of the deprotonated hydrogen‐bonded complexes F^−^(HF), F^−^(H~2~O), F^−^(NH~3~), Cl^−^(HF), SH^−^(HF), H~2~P^−^(HF), OH^−^(H~2~O), OH^−^(H~2~O)~2~, OH^−^(NH~3~), Cl^−^(H~2~O), SH^−^(H~2~O), H~2~P^−^(H~2~O), Cl^−^(NH~3~), SH^−^(NH~3~), H~2~P^−^(NH

Reduction of the basis set superposition
Reduction of the basis set superposition error at the correlation level
✍ Peter Wind; Jean-Louis Heully 📂 Article 📅 1994 🏛 Elsevier Science 🌐 English ⚖ 526 KB

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