Basis‐set completeness profiles in two dimensions

Abstract

Abstract A two‐electron basis‐set completeness profile is proposed by analogy with the one‐electron profile introduced by D. P. Chong (Can J Chem 1995, 73, 79). It is defined as Y(α,β)=∑_m∑_n〈G_α(1)G_β(2)∣(1/r₁₂)∣Ψ_m(1)Ψ_n(2)〉〈Ψ_m(1)Ψ_n(2)∣r₁₂∣G_α(1)G_β(2)〉 and motivated by the expression for the basis‐set truncation correction that occurs in the framework of explicitly correlated methods (G_α is a scanning Gaussian‐type orbital of exponent α and {Ψ_m} is the orthonormalized one‐electron basis under study). The two‐electron basis‐set profiles provide a visual assessment of the suitability of basis sets to describe electron‐correlation effects. Furthermore, they provide the opportunity to assess the quality of the basis set as a whole—not only of the individual angular momentum subspaces, as is the case for the one‐electron basis‐set profiles. The two‐electron completeness profiles of the cc‐pVXZ (X=D, T, Q), aug‐cc‐pVTZ, cc‐pCVTZ, and SVP‐auxiliary basis sets for the carbon atom are presented as illustrative examples. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 420–425, 2002