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Gaussian basis sets for use in correlated molecular calculations. V. Core-valence basis sets for boron through neon

J. Chem. Phys. 103, 4572 (1995); doi:10.1063/1.470645

Issue Date: 15 September 1995

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David E. Woon and Thom H. Dunning, Jr.
Theory, Modeling and Simulation, Environmental Molecular Sciences Laboratory, Pacific Northwest Laboratory, Richland, Washington 99352
The correlation-consistent polarized valence basis sets (cc-pVXZ) for the atoms boron through neon have been extended to treat core and core-valence correlation effects. Basis functions were added to the existing cc-pVXZ sets to form correlation-consistent polarized core-valence sets (cc-pCVXZ) in the usual pattern: Double zeta added (1s1p), triple zeta added (2s2p1d), quadruple zeta added (3s3p2d1f), and quintuple zeta added (4s4p3d2f1g). The exponents of the core functions were determined by minimizing the difference between all-electron and valence-only correlation energies obtained from HF+1+2 calculations on the ground states of the atoms. With the cc-pCVXZ sets, core, core-valence, and valence correlation energies all converge exponentially toward apparent complete basis set (CBS) limits, as do the corresponding all-electron singles and doubles CI energies. Several test applications of the new sets are presented: The first two ionization potentials of boron, the 3P–5S separation in carbon, and the X-tilde 3B1–a-tilde 1A1 state separation in CH2. As expected, correlation effects involving the core electrons of the first row atoms, B–Ne, are small but must be included if high accuracy is required. ©1995 American Institute of Physics.
History: Received 20 April 1995; accepted 6 June 1995
Permalink: http://link.aip.org/link/?JCPSA6/103/4572/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.Rh
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Valence bond calculations
  • 31.25.Eb
    Electronic structure of atoms, molecules and their ions: theory Electron correlation calculations for atoms and molecules Electron-correlation calculations for atoms and ions: ground state
  • YEAR: 1995

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (23)
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  1. P. R. Taylor, in Lecture Notes in Quantum Chemistry, edited by B. O. Roos (Springer-Verlag, Berlin, 1992), p. 406.
  2. (a) T. H. Dunning, Jr., J. Chem. Phys. 90, 1007 (1989);
    3. (b) R. A. Kendall, T. H. Dunning, Jr., and R. J. Harrison, ibid. 96, 6796 (1992);
    (c) D. E. Woon and T. H. Dunning, Jr., ibid. 98, 1358 (1993);
    (d) 100, 2975 (1994).
  3. D. E. Woon and T. H. Dunning, Jr. (in preparation).
  4. C. W. Bauschlicher, Jr., S. R. Langhoff, and P. R. Taylor, J. Chem. Phys. 88, 2540 (1988).
  5. H. Partridge, C. W. Bauschlicher, Jr., S. P. Walch, and B. Liu, J. Chem. Phys. 79, 1866 (1983).
  6. (a) D. E. Woon and T. H. Dunning, Jr., J. Chem. Phys. 99, 1914 (1993);
    7. (b) K. A. Peterson, R. A. Kendall, and T. H. Dunning, Jr., J. Chem. Phys. 99, 1930 (1993);
    (c) 99, 9790 (1993);
    (d) D. E. Woon and T. H. Dunning, Jr., J. Chem. Phys. 101, 8877 (1994).
  7. F. Sasaki and M. Yoshimine, Phys. Rev. A 9, 17 (1974).
  8. (a) P. J. Knowles, C. Hampel, and H.-J. Werner, J. Chem. Phys. 99, 5219 (1993) and references therein;
    9. (b) M. J. O. Deegan and P. J. Knowles, Chem. Phys. Lett. 227, 321 (1994).
  9. K. A. Peterson, D. E. Woon, and T. H. Dunning, Jr. (in preparation).
  10. MOLPRO is a suite of ab initio programs written by H.-J. Werner and P. J. Knowles with contributions by J. Almlöf, R. D. Amos, M. J. O. Deegan, S. T. Elbert, C. Hampel, W. Meyer, K. A. Peterson, R. M. Pitzer, A. J. Stone, and P. R. Taylor.
  11. H.-J. Werner and P. J. Knowles, J. Chem. Phys. 89, 5803 (1988);
    12. P. J. Knowles and H.-J. Werner, Chem. Phys. Lett. 145, 514 (1988).
  12. H.-J. Werner and P. J. Knowles, J. Chem. Phys. 82, 5053 (1985);
    13. P. J. Knowles and H.-J. Werner, Chem. Phys. Lett. 115, 259 (1985).
  13. (a) S. R. Langhoff and E. R. Davidson, Int. J. Quantum Chem. 8, 61 (1974);
    14. (b) E. R. Davidson and D. W. Silver, Chem. Phys. Lett. 53, 403 (1977).
  14. C. Hampel, K. A. Peterson, and H.-J. Werner, Chem. Phys. Lett. 190, 1 (1992) and references therein.
  15. R. C. Raffenetti, J. Chem. Phys. 58, 4452 (1973).
  16. For oxygen, separate groups of functions were optimized for the CC pair (1s2) and for the CV pairs (1s2s,1s2p). As detailed later in the text, optimization for CC correlation leads to a correlation consistent family of functions. However, when functions are optimized for CV correlation, the convergence is not monotonic and it is not possible to distinguish well defined, correlation consistent groupings.
  17. A. Veillard and E. Clementi, J. Chem. Phys. 49, 2415 (1968).
  18. C. E. Moore, Atomic Energy Levels, Vol. I (Office of Standard Reference Data, National Bureau of Standards, Washington, D.C., 1971), Circ. No. 35.
  19. CI wave functions are designated by appending “+1+2” to the relevant reference function.
  20. J. Senekowitsch, Ph.D. thesis, Universitat Frankfurt, Frankfurt, Germany, 1988.
  21. A. D. McLean, P. R. Bunker, R. M. Escribano, and P. Jensen, J. Chem. Phys. 87, 2166 (1987).
  22. To use anonymous ftp to retrieve the basis sets, execute the following commands: ftp pnlg.pnl.gov/login as ANONYMOUS/provide your e-mail address as the password/cd CCBASIS/get<desired files>. Download README.DOC for further information.
  23. The URL for the order form for the new core-valence correlation consistent basis sets is http://www.emsl.pnl.gov:2080/forms/basisform.html. Follow the instructions on the form to select the desired basis set(s) and have them e-mailed to you.

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