The Effect of Basis Set Superposition Error (BSSE) on the Convergence of Molecular Properties Calculated with the Correlation Consistent Basis Sets

Tanja Van Mourik, Angela K. Wilson, Kirk A. Peterson, David E. Woon, Thom H. Dunning

Research output: Contribution to journalArticlepeer-review

Abstract

It is shown that, in many cases, the convergence behavior of molecular properties computed with the correlation consistent basis sets (both standard and augmented sets) is significantly improved if basis set superposition error (BSSE) is taken into account. The effects are most pronounced for pure van der Waals systems like the helium or argon dimers. For these systems the uncorrected De, re, and ωe behave very irregularly with increasing basis set size, with the convergence behavior being dramatically improved by use of the counterpoise procedure. Even for strongly bound diatomics like N2, HF, and HCl, the counterpoise correction often significantly improves the convergence behavior of re and ωe. Similar behavior is observed in the weakly bound molecular complexes, ArHF, HCO-, and (HF)2, as well as for the more strongly bound HCO molecule. For HCO-, because of the pronounced lengthening of the CO bond upon molecular formation, the deformation energy must also be taken into account.

Original languageEnglish (US)
Pages (from-to)105-135
Number of pages31
JournalAdvances in Quantum Chemistry
Volume31
Issue numberC
DOIs
StatePublished - Dec 1 1998
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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