Abstract
Least-squares representations of the 3s and 3p Slater-type atomic orbitals by a small number of Gaussian functions are presented. The use of these Gaussian representations in self-consistent molecular orbital calculations extends our previous study to molecules containing second row elements. Calculated atomization energies, electric dipole moments, and atomic charges are shown to rapidly converge (with increasing number of Gaussians) to their Slater limits. Results of valence shell optimization studies on a series of second-row compounds are nearly independent of the level of the Gaussian approximation, and they allow a set of standard molecular ξ exponents to be proposed.
Keywords
Slater-type orbitalGaussianMolecular orbitalAtomic orbitalMolecular orbital theoryDipoleSTO-nG basis setsLinear combination of atomic orbitalsValence (chemistry)Extension (predicate logic)Atomic physicsBasis setChemistryComputational chemistryMoleculePhysicsQuantum mechanicsElectronComputer science
Affiliated Institutions
Related Publications
Self-Consistent Molecular-Orbital Methods. I. Use of Gaussian Expansions of Slater-Type Atomic Orbitals
Least-squares representations of Slater-type atomic orbitals as a sum of Gaussian-type orbitals are presented. These have the special feature that common Gaussian exponents are ...
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
Two extended basis sets (termed 5–31G and 6–31G) consisting of atomic orbitals expressed as fixed linear combinations of Gaussian functions are presented for the first row atoms...
Self-Consistent Molecular Orbital Methods. VI. Energy Optimized Gaussian Atomic Orbitals
Minimal basis atomic orbitals expressed as sums of N Gaussian functions are presented for hydrogen and for the first row atoms boron to fluorine. The expansion coefficients and ...
Charge separation and covalent bonding in metal oxide surfaces: A local density functional study on the MgO(001) surface
A first principles local density functional investigation on extended, two-dimensional periodic slab models of the MgO(001) surface is performed, using the linear combination of...
Electronic Spectra of Isoelectronic Amides, Acids, and Acyl Fluorides
The first four bands in the gas-phase spectra of amides, carboxylic acids, and acyl fluorides are thought to be n → π*, n → 3s Rydberg, π → π*, and n → 3p Rydberg excitations. T...
Publication Info
- Year
- 1970
- Type
- article
- Volume
- 52
- Issue
- 5
- Pages
- 2769-2773
- Citations
- 703
- Access
- Closed
External Links
Social Impact
Altmetric
PlumX Metrics
Social media, news, blog, policy document mentions
Citation Metrics
703
OpenAlex
Cite This
Warren J. Hehre,
R. Ditchfield,
R. F. Stewart
et al.
(1970).
Self-Consistent Molecular Orbital Methods. IV. Use of Gaussian Expansions of Slater-Type Orbitals. Extension to Second-Row Molecules.
The Journal of Chemical Physics
, 52
(5)
, 2769-2773.
https://doi.org/10.1063/1.1673374
Identifiers
- DOI
- 10.1063/1.1673374