Systematically Convergent Correlation Consistent Basis Sets for Molecular Core−Valence Correlation Effects: The Third-Row Atoms Gallium through Krypton

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Abstract

The family of correlation consistent polarized valence basis sets has been extended in order to account for core-core and core-valence correlation effects within the third-row, main group atoms gallium through krypton. Construction of the basis sets is similar to that of the atoms boron through argon, where either the difference between core-correlated and valence-only correlation energies were calculated via configuration interaction (CISD) computations on the ground electronic states of the atoms (named cc-pCVnZ) or the sets were optimized with respect to the core-valence correlation energy and a small weight of core-core correlation energy (cc-pwCVnZ). Due to the correlation of 3d orbitals, added shells of higher angular momentum exponents compared to the valence sets are necessary to describe the core region. The pattern of added core-correlating functions is (1s1p1d1f) for double-zeta, (2s2p2d2f1g) for triple-zeta, (3s3p3d3f2g1h) for quadruple-zeta, and (4s4p4d4f3g2h1i) for quintuple-zeta. Atomic and molecular results show good convergence to the CBS limit, with the cc-pwCVnZ sets showing improved convergence compared to the cc-pCVnZ ones for molecular core-valence correlation effects. After testing the basis sets on the homonuclear diatomics Ga2-Kr2 with coupled cluster wave functions, it is concluded that a treatment of core-valence correlation effects is essential for high-accuracy ab initio investigations of third-row-containing molecules. Though the basis sets are optimal for 3s3p3d correlation, preliminary atomic and molecular results show the basis sets to be efficient with respect to 3d-only correlation, and these potentially could be used with 3d-only correlation for more qualitative studies on larger species.

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