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The electron affinity of oxygen: A systematic configuration interaction approach
A sequence of configuration interaction (CI) wave functions, constructed so as to systematically approach the complete basis set, full CI limit, is used to argue that the only alternatives for improvi...

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen

J. Chem. Phys. 90, 1007 (1989); doi:10.1063/1.456153

Issue Date: 15 January 1989

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Thom H. Dunning, Jr.
Theoretical & Computational Chemistry Group, Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439
In the past, basis sets for use in correlated molecular calculations have largely been taken from single configuration calculations. Recently, Almlöf, Taylor, and co-workers have found that basis sets of natural orbitals derived from correlated atomic calculations (ANOs) provide an excellent description of molecular correlation effects. We report here a careful study of correlation effects in the oxygen atom, establishing that compact sets of primitive Gaussian functions effectively and efficiently describe correlation effects if the exponents of the functions are optimized in atomic correlated calculations, although the primitive (sp) functions for describing correlation effects can be taken from atomic Hartree–Fock calculations if the appropriate primitive set is used. Test calculations on oxygen-containing molecules indicate that these primitive basis sets describe molecular correlation effects as well as the ANO sets of Almlöf and Taylor. Guided by the calculations on oxygen, basis sets for use in correlated atomic and molecular calculations were developed for all of the first row atoms from boron through neon and for hydrogen. As in the oxygen atom calculations, it was found that the incremental energy lowerings due to the addition of correlating functions fall into distinct groups. This leads to the concept of correlation consistent basis sets, i.e., sets which include all functions in a given group as well as all functions in any higher groups. Correlation consistent sets are given for all of the atoms considered. The most accurate sets determined in this way, [5s4p3d2f1g], consistently yield 99% of the correlation energy obtained with the corresponding ANO sets, even though the latter contains 50% more primitive functions and twice as many primitive polarization functions. It is estimated that this set yields 94%–97% of the total (HF+1+2) correlation energy for the atoms neon through boron. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 26 July 1988; accepted 28 September 1988
Permalink: http://link.aip.org/link/?JCPSA6/90/1007/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.20.Tz
    Electronic structure of atoms and molecules: theory Specific calculations and results Electron correlation and CI calculations
  • 31.20.Ej
    Electronic structure of atoms and molecules: theory Specific calculations and results Ab initio MO calculations
  • YEAR: 1988-89

PUBLICATION DATA

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

REFERENCES (37)
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