Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon

TLDR

The authors extended Dunning’s correlation‑consistent methodology to the second‑row p‑block atoms, optimizing polarization exponents for correlated HF+1+2 wave functions and defining double, triple, and quadruple‑zeta basis sets that are further augmented with diffuse functions optimized on anion HF energies. Correlation‑consistent and augmented correlation‑consistent basis sets were established for aluminum through argon, with (sp) correlation functions from HF primitives showing minimal deviation from optimum, and sulfur results guiding the construction of the remaining second‑row sets. Phys.

Abstract

Correlation consistent and augmented correlation consistent basis sets have been determined for the second row atoms aluminum through argon. The methodology, originally developed for the first row atoms [T. H. Dunning, Jr., J. Chem. Phys. 90, (1989)] is first applied to sulfur. The exponents for the polarization functions (dfgh) are systematically optimized for a correlated wave function (HF+1+2). The (sp) correlation functions are taken from the appropriate HF primitive sets; it is shown that these functions differ little from the optimum functions. Basis sets of double zeta [4s3p1d], triple zeta [5s4p2d1f], and quadruple zeta [6s5p3d2f1g] quality are defined. Each of these sets is then augmented with diffuse functions to better describe electron affinities and other molecular properties: s and p functions were obtained by optimization for the anion HF energy, while an additional polarization function for each symmetry present in the standard set was optimized for the anion HF+1+2 energy. The results for sulfur are then used to assist in determining double zeta, triple zeta, and quadruple zeta basis sets for the remainder of the second row of the p block.