Literature DB >> 26579908

Can the Counterpoise Correction for Basis Set Superposition Effect Be Justified?

Ł M Mentel1,2, E J Baerends1,2,3.   

Abstract

The basis set superposition effect (BSSE) is a simple concept, and its validity is almost universally accepted. So is the counterpoise method to correct for it. The idea is that the basis set is biased toward the dimer because each monomer in the dimer can "use" the basis functions on the other monomer, which it cannot in a simple monomer calculation. This hypothesis can only be tested if basis set free benchmark numbers are available for monomers and dimer. We are testing the hypothesis on a few systems (in this paper Be2) that are small enough that sufficiently accurate benchmark numbers (basis set free, or close to basis set limit; full CI or close to full CI) are available or can be obtained. We find that the answer to the title question is negative: the standard basis sets of quantum chemistry appear to be biased toward the atom in the sense that basis set errors are larger for the dimer than the monomer. Applying the counterpoise correction increases the imbalance by reducing the already smaller basis set error of the monomer even further. Counterpoise corrected bond energies then deviate more from the basis set limit numbers than uncorrected bond energies. These conclusions hold both at the Hartree-Fock level and (much stronger) at the correlated (CCSD(T), full CI) levels. So the answer to the title question is No.

Year:  2013        PMID: 26579908     DOI: 10.1021/ct400990u

Source DB:  PubMed          Journal:  J Chem Theory Comput        ISSN: 1549-9618            Impact factor:   6.006


  13 in total

1.  Theoretical study of interactions between electron-deficient arenes and coinage metal anions.

Authors:  Yishan Chen; Fan Wang
Journal:  J Mol Model       Date:  2015-02-08       Impact factor: 1.810

2.  The interaction strengths and spectroscopy parameters of the C2H2∙∙∙HX and HCN∙∙∙HX complexes (X = F, Cl, CN, and CCH) and related ternary systems valued by fluxes of charge densities: QTAIM, CCFO, and NBO calculations.

Authors:  Marco A A Viana; Regiane C M U Araújo; José A Maia Neto; Henrique C Chame; Arquimedes M Pereira; Boaz G Oliveira
Journal:  J Mol Model       Date:  2017-03-11       Impact factor: 1.810

3.  Testing the CP-correction procedure with different DFT methods on H-bonding complexes of κ-carrabiose with water molecules.

Authors:  Rachida Fodil; Majda Sekkal-Rahal; Adlane Sayede
Journal:  J Mol Model       Date:  2017-01-14       Impact factor: 1.810

4.  First-principles calculations of hybrid inorganic-organic interfaces: from state-of-the-art to best practice.

Authors:  Oliver T Hofmann; Egbert Zojer; Lukas Hörmann; Andreas Jeindl; Reinhard J Maurer
Journal:  Phys Chem Chem Phys       Date:  2021-03-25       Impact factor: 3.676

Review 5.  Small Atomic Orbital Basis Set First-Principles Quantum Chemical Methods for Large Molecular and Periodic Systems: A Critical Analysis of Error Sources.

Authors:  Rebecca Sure; Jan Gerit Brandenburg; Stefan Grimme
Journal:  ChemistryOpen       Date:  2015-11-25       Impact factor: 2.911

Review 6.  Quantum Chemical Modeling of Hydrogen Bonding in Ionic Liquids.

Authors:  Patricia A Hunt
Journal:  Top Curr Chem (Cham)       Date:  2017-05-18

7.  Predicting the Ionic Product of Water.

Authors:  Eva Perlt; Michael von Domaros; Barbara Kirchner; Ralf Ludwig; Frank Weinhold
Journal:  Sci Rep       Date:  2017-08-31       Impact factor: 4.379

8.  Dimerization of Acetic Acid in the Gas Phase-NMR Experiments and Quantum-Chemical Calculations.

Authors:  Ondřej Socha; Martin Dračínský
Journal:  Molecules       Date:  2020-05-04       Impact factor: 4.411

9.  Quantitative Assessment of Tetrel Bonding Utilizing Vibrational Spectroscopy.

Authors:  Daniel Sethio; Vytor Oliveira; Elfi Kraka
Journal:  Molecules       Date:  2018-10-25       Impact factor: 4.411

10.  On the Use of Popular Basis Sets: Impact of the Intramolecular Basis Set Superposition Error.

Authors:  Ángel Vidal Vidal; Luis Carlos de Vicente Poutás; Olalla Nieto Faza; Carlos Silva López
Journal:  Molecules       Date:  2019-10-22       Impact factor: 4.411

View more

北京卡尤迪生物科技股份有限公司 © 2022-2023.