DOI: 10.1063/1.1678187. Near Hartree-Fock Calculations on the Ground State of the Water Molecule: Energies, Ionization Potentials, Geometry, Force Constants, and One-Electron Properties

Near Hartree-Fock Calculations on the Ground State of the Water Molecule: Energies, Ionization Potentials, Geometry, Force Constants, and One-Electron Properties

10.1063/1.1678187

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Near Hartree-Fock wavefunctions have been calculated for the ground state of the water molecule using both Slater and contracted Gaussian basis sets. Total energies of −76.063 hartree were obtained with a (5s4p1d/3s1p) Slater basis and a [6s5p2d/3s1p] contracted Gaussian basis derived from an (11s7p2d/5s1p) primitive set; these energies are estimated to be within 0.003±0.002 hartree of the Hartree-Fock limit. The Hartree-Fock wavefunctions account for ∼70% of the dissociation energy of water. The Hartree-Fock vertical ionization potentials (in electron volts), 11.1(2B1), 13.3(2A1), and 17.6(2B2), are too low by 1–1.5 eV as expected. With the Gaussian basis set a potential surface was computed and the equilibrium geometry and harmonic force constants were calculated. The calculated bond length, 0.941 Å, and bond angle 106.6°, are in good agreement with the experimental values, 0.957 Å and 104.52°. In spite of the rather good agreement for the geometry, the force constants are in error by 15%–20%. This is attributed to an inadequancy of the Hartree-Fock model. A number of one-electron properties were also computed; they differ only slightly from those reported in earlier work and are in satisfactory agreement with experiment. Plots of the valence (canonical) molecular orbitals are given.

Bibliography

Dunning, Thom. H., Pitzer, R. M., & Aung, S. (1972). Near Hartree-Fock Calculations on the Ground State of the Water Molecule: Energies, Ionization Potentials, Geometry, Force Constants, and One-Electron Properties. The Journal of Chemical Physics, 57(12), 5044â5051.

Authors 3

Thom. H. Dunning (first)
Russell M. Pitzer (additional)
Soe Aung (additional)

References 32 Referenced 143

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Dates

Type	When
Created	21 years, 6 months ago (Feb. 6, 2004, 4:02 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 5:50 a.m.)
Indexed	4 months ago (April 30, 2025, 12:09 a.m.)
Issued	52 years, 8 months ago (Dec. 15, 1972)
Published	52 years, 8 months ago (Dec. 15, 1972)
Published Print	52 years, 8 months ago (Dec. 15, 1972)

Funders 0

None

BibTeX

@article{Dunning_1972, title={Near Hartree-Fock Calculations on the Ground State of the Water Molecule: Energies, Ionization Potentials, Geometry, Force Constants, and One-Electron Properties}, volume={57}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1678187}, DOI={10.1063/1.1678187}, number={12}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Dunning, Thom. H. and Pitzer, Russell M. and Aung, Soe}, year={1972}, month=dec, pages={5044–5051} }

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  "abstract": "<jats:p>Near Hartree-Fock wavefunctions have been calculated for the ground state of the water molecule using both Slater and contracted Gaussian basis sets. Total energies of \u221276.063 hartree were obtained with a (5s4p1d/3s1p) Slater basis and a [6s5p2d/3s1p] contracted Gaussian basis derived from an (11s7p2d/5s1p) primitive set; these energies are estimated to be within 0.003\u00b10.002 hartree of the Hartree-Fock limit. The Hartree-Fock wavefunctions account for \u223c70% of the dissociation energy of water. The Hartree-Fock vertical ionization potentials (in electron volts), 11.1(2B1), 13.3(2A1), and 17.6(2B2), are too low by 1\u20131.5 eV as expected. With the Gaussian basis set a potential surface was computed and the equilibrium geometry and harmonic force constants were calculated. The calculated bond length, 0.941 \u00c5, and bond angle 106.6\u00b0, are in good agreement with the experimental values, 0.957 \u00c5 and 104.52\u00b0. In spite of the rather good agreement for the geometry, the force constants are in error by 15%\u201320%. This is attributed to an inadequancy of the Hartree-Fock model. A number of one-electron properties were also computed; they differ only slightly from those reported in earlier work and are in satisfactory agreement with experiment. Plots of the valence (canonical) molecular orbitals are given.</jats:p>",
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