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

Journal Article · Fri Oct 01 00:00:00 EDT 1982 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.444267· OSTI ID:6695534

Francl, M M; Pietro, W J; Hehre, W J; Binkley, J S; Gordon, M S; DeFrees, D J; Pople, J A

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.

• Research Organization: Department of Chemistry, University of California, Irvine, California 92717
• OSTI ID: 6695534
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 77:7; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ALKALI METALS
ALKALINE EARTH METALS
BERYLLIUM
BORON
CARBON
ELECTRONIC STRUCTURE
ELEMENTS
FLUIDS
FLUORINE
FUNCTIONS
GASES
HALOGENS
HYDRIDES
HYDROGEN COMPOUNDS
LITHIUM
METALS
MOLECULAR ORBITAL METHOD
MOLECULAR STRUCTURE
NEON
NITROGEN
NONMETALS
OXYGEN
RARE GASES
SELF-CONSISTENT FIELD
SEMIMETALS
WAVE FUNCTIONS