J. Stephen Binkley

A contracted Gaussian basis set (6-311G**) is developed by optimizing exponents and coefficients at the Mo/ller–Plesset (MP) second-order level for the ground states of first-row atoms. This has a triple split in the valence s and p shells together with a single set of uncontracted polarization functions on each atom. The basis is tested by computing structures and energies for some simple molecules at various levels of MP theory and comparing with experiment.

Standard sets of supplementary diffuse s and p functions, multiple polarization functions (double and triple sets of d functions), and higher angular momentum polarization functions (f functions) are defined for use with the 6-31G and 6-311G basis sets. Preliminary applications of the modified basis sets to the calculation of the bond energy and hydrogenation energy of N2 illustrate that these functions can be very important in the accurate computation of reaction energies.

The 6-31G* and 6-31G** basis sets previously introduced for first-row atoms have been extended through the second-row of the periodic table. Equilibrium geometries for one-heavy-atom hydrides calculated for the two-basis sets and using Hartree–Fock wave functions are in good agreement both with each other and with the experimental data. HF/6-31G* structures, obtained for two-heavy-atom hydrides and for a variety of hypervalent second-row molecules, are also in excellent accord with experimental equilibrium geometries. No large deviations between calculated and experimental single bond lengths have been noted, in contrast to previous work on analogous first-row compounds, where limiting Hartree–Fock distances were in error by up to a tenth of an angstrom. Equilibrium geometries calculated at the HF/6-31G level are consistently in better agreement with the experimental data than are those previously obtained using the simple split-valance 3-21G basis set for both normal- and hypervalent compounds. Normal-mode vibrational frequencies derived from 6-31G* level calculations are consistently larger than the corresponding experimental values, typically by 10%–15%; they are of much more uniform quality than those obtained from the 3-21G basis set. Hydrogenation energies calculated for normal- and hypervalent compounds are in moderate accord with experimental data, although in some instances large errors appear. Calculated energies relating to the stabilities of single and multiple bonds are in much better accord with the experimental energy differences.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSelf-consistent molecular orbital methods. 21. Small split-valence basis sets for first-row elementsJ. Stephen Binkley, John A. Pople, and Warren J. HehreCite this: J. Am. Chem. Soc. 1980, 102, 3, 939–947Publication Date (Print):January 1, 1980Publication History Published online1 May 2002Published inissue 1 January 1980https://pubs.acs.org/doi/10.1021/ja00523a008https://doi.org/10.1021/ja00523a008research-articleACS PublicationsRequest reuse permissionsArticle Views3442Altmetric-Citations3561LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSelf-consistent molecular-orbital methods. 22. Small split-valence basis sets for second-row elementsMark S. Gordon, J. Stephen Binkley, John A. Pople, William J. Pietro, and Warren J. HehreCite this: J. Am. Chem. Soc. 1982, 104, 10, 2797–2803Publication Date (Print):May 1, 1982Publication History Published online1 May 2002Published inissue 1 May 1982https://pubs.acs.org/doi/10.1021/ja00374a017https://doi.org/10.1021/ja00374a017research-articleACS PublicationsRequest reuse permissionsArticle Views1406Altmetric-Citations1554LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts