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.

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T. H. Dunning, Jr. (unpublished). Calculations were performed using the atomic Hartree-Fock-Roothaan program of E. Clementi as modified by T. H. Dunning, Jr. and R. M. Pitzer.
15.
C. Froese Fischer, The Hartree-Fock Method for Atoms. A Numerical Approach (Wiley, New York, 1977), Chap. 2.
16.
MOLPRO is a package of ab initio programs written by H.-J. Werner and P. J. Knowles, with contributions from J. Almlöf, R. Amos, S. Elbert, W. Meyer, E.-A. Reinsch, R. Pitzer, and A. Stone;
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17.
MELDF-X was originally written by L. McMurchie, S. Elbert, S. LanghofF, and E. R. Davidson;
it has been substantially modified by D. Feller, R. Cave, D. Rawlings, R. Frey, R. Daasch, I. Nitche, P. Phillips, C. Jackels, and E. R. Davidson.
18.
The number arising from this calculation, which was calculated using MOLPRO, is on a slightly different footing than the other values because MOLPRO does not allow configurations to be generated from all three equivalent configurations. To be consistent MOLPRO was used to calculate the CISD numbers for both the [4d3f2g] and [4d3f2g1h] calculations.
19.
The h function contribution for the oxygen cc-pV5Z set was determined by K. A. Peterson (unpublished).
20.
The smaller (20s) primitive set was used in this section due to a limit of 20 functions per s contraction in MELDF.
21.
(a)
S. S.
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and
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(b) S. S. Xantheas and T. H. Dunning, Jr. (private communication).
22.
D. E. Woon and T. H. Dunning, Jr. (to be published).
23.
The total contributions for polarization functions in Tables VIII and IX differ slightly. The former values were determined using identical HF orbitals and (sp) correlation functions throughout, while the latter numbers were computed using HF orbitals and (sp) correlation functions which improved as the size of the polarization function set was increased. Nevertheless, the largest discrepancy (in argon) is 0.167 mhartree out of −185.572 mhartree.
24.
The trends in the exponents of the augmenting functions behave slightly differently for Al-P vs S and Cl, due to whether the ground state of the atom does or does not have unpaired 3p electrons.
25.
The correlation consistent and augmented correlation consistent basis sets for the first and second row atoms (plus hydrogen and helium) may be obtained by sending a request through electronic mail to D. Feller 〈d3el02@pnlg.pnl.gov〉 or D. E. W. 〈ng436@pnlg.pnl.gov〉. They may also be downloaded via anonymous ftp through pnlg.pnl.gov: ftp pnlg.pnl.gov login as ANONYMOUS (provide e-mail address when asked for password) cd CCBASIS get 〈files〉 Download README.DOC for further information.
26.
D. E. Woon, K. A. Peterson, and T. H. Dunning, Jr. (to be published).
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