A full-CI investigation into the BSSE problem

I. Mayer, A. Vibók, P. Valiron

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

Full-CI calculations have been performed on the four-electron model systems He...He and H2...H2 in order to compare the a posteriori Boys-Bernardi (counterpoise) and the a priori CHA ('chemical Hamiltonian approach') schemes for correcting BSSE ('basis set superposition error') at the electron correlation level. The results indicate that the CHA scheme performs excellently for correlated systems: analogously to the previous SCF calculations, the Boys-Bernardi and the CHA schemes lead to similar results. The correlation contributions to the interaction energy are especially close; the Boys-Bernardi scheme exhibits a slight 'overcompensation' effect in the van der Waals region, as could be expected. The counterpoise-corrected Møller-Plesset MP2 and MP4 perturbational results are also compared with the full-CI ones and a proposition is put forward for a proper definition of the quantity 'BSSE-free interaction energy in a given basis'.

Original languageEnglish
Pages (from-to)166-174
Number of pages9
JournalChemical Physics Letters
Volume224
Issue number1-2
DOIs
Publication statusPublished - Jul 8 1994

Fingerprint

Hamiltonians
Electron correlations
self consistent fields
electrons
interactions
energy
Electrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • Surfaces and Interfaces

Cite this

A full-CI investigation into the BSSE problem. / Mayer, I.; Vibók, A.; Valiron, P.

In: Chemical Physics Letters, Vol. 224, No. 1-2, 08.07.1994, p. 166-174.

Research output: Contribution to journalArticle

Mayer, I. ; Vibók, A. ; Valiron, P. / A full-CI investigation into the BSSE problem. In: Chemical Physics Letters. 1994 ; Vol. 224, No. 1-2. pp. 166-174.
@article{753bed2325294f9ba7cd4c43c9c3c743,
title = "A full-CI investigation into the BSSE problem",
abstract = "Full-CI calculations have been performed on the four-electron model systems He...He and H2...H2 in order to compare the a posteriori Boys-Bernardi (counterpoise) and the a priori CHA ('chemical Hamiltonian approach') schemes for correcting BSSE ('basis set superposition error') at the electron correlation level. The results indicate that the CHA scheme performs excellently for correlated systems: analogously to the previous SCF calculations, the Boys-Bernardi and the CHA schemes lead to similar results. The correlation contributions to the interaction energy are especially close; the Boys-Bernardi scheme exhibits a slight 'overcompensation' effect in the van der Waals region, as could be expected. The counterpoise-corrected M{\o}ller-Plesset MP2 and MP4 perturbational results are also compared with the full-CI ones and a proposition is put forward for a proper definition of the quantity 'BSSE-free interaction energy in a given basis'.",
author = "I. Mayer and A. Vib{\'o}k and P. Valiron",
year = "1994",
month = "7",
day = "8",
doi = "10.1016/0009-2614(94)00523-0",
language = "English",
volume = "224",
pages = "166--174",
journal = "Chemical Physics Letters",
issn = "0009-2614",
publisher = "Elsevier",
number = "1-2",

}

TY - JOUR

T1 - A full-CI investigation into the BSSE problem

AU - Mayer, I.

AU - Vibók, A.

AU - Valiron, P.

PY - 1994/7/8

Y1 - 1994/7/8

N2 - Full-CI calculations have been performed on the four-electron model systems He...He and H2...H2 in order to compare the a posteriori Boys-Bernardi (counterpoise) and the a priori CHA ('chemical Hamiltonian approach') schemes for correcting BSSE ('basis set superposition error') at the electron correlation level. The results indicate that the CHA scheme performs excellently for correlated systems: analogously to the previous SCF calculations, the Boys-Bernardi and the CHA schemes lead to similar results. The correlation contributions to the interaction energy are especially close; the Boys-Bernardi scheme exhibits a slight 'overcompensation' effect in the van der Waals region, as could be expected. The counterpoise-corrected Møller-Plesset MP2 and MP4 perturbational results are also compared with the full-CI ones and a proposition is put forward for a proper definition of the quantity 'BSSE-free interaction energy in a given basis'.

AB - Full-CI calculations have been performed on the four-electron model systems He...He and H2...H2 in order to compare the a posteriori Boys-Bernardi (counterpoise) and the a priori CHA ('chemical Hamiltonian approach') schemes for correcting BSSE ('basis set superposition error') at the electron correlation level. The results indicate that the CHA scheme performs excellently for correlated systems: analogously to the previous SCF calculations, the Boys-Bernardi and the CHA schemes lead to similar results. The correlation contributions to the interaction energy are especially close; the Boys-Bernardi scheme exhibits a slight 'overcompensation' effect in the van der Waals region, as could be expected. The counterpoise-corrected Møller-Plesset MP2 and MP4 perturbational results are also compared with the full-CI ones and a proposition is put forward for a proper definition of the quantity 'BSSE-free interaction energy in a given basis'.

UR - http://www.scopus.com/inward/record.url?scp=0000047371&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000047371&partnerID=8YFLogxK

U2 - 10.1016/0009-2614(94)00523-0

DO - 10.1016/0009-2614(94)00523-0

M3 - Article

AN - SCOPUS:0000047371

VL - 224

SP - 166

EP - 174

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

IS - 1-2

ER -