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Self-consistent molecular orbital methods. XXIII. A polarization-type basis set for second-row elements

1982/10/01 by Michelle Francl, Michelle M. Francl, William J. Pietro +5 · 8,213 citations
Chemistry · Mathematics · Physics and Astronomy · #Advanced Chemical Physics Studies #Atom (system on chip) #Atomic physics #Basis (linear algebra) #Basis set #Bond length #Chemistry #Computational chemistry #Density functional theory #Geometry #Hartree–Fock method #Hypervalent molecule #Inorganic Chemistry and Materials #Inorganic Fluorides and Related Compounds #Mathematics #Molecular geometry #Molecular orbital #Molecular physics #Molecule #Physical chemistry #Physics

paper · open access · doi:10.1063/1.444267

published in The Journal of Chemical Physics 77(7), 3654-3665 (American Institute of Physics)

openalex publication_date 1982/10/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

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.

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