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 shared between Slater‐type and functions. Use of these atomic orbitals in self‐consistent molecular‐orbital calculations is shown to lead to values of atomization energies, atomic populations, and electric dipole moments which converge rapidly (with increasing size of Gaussian expansion) to the values appropriate for pure Slater‐type orbitals. The exponents (or scale factors) for the atomic orbitals which are optimized for a number of molecules are also shown to be nearly independent of the number of Gaussian functions. A standard set of values for use in molecular calculations is suggested on the basis of this study and is shown to be adequate for the calculation of total and atomization energies, but less appropriate for studies of charge distribution.
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15 September 1969
Research Article|
September 15 1969
Self‐Consistent Molecular‐Orbital Methods. I. Use of Gaussian Expansions of Slater‐Type Atomic Orbitals
W. J. Hehre;
W. J. Hehre
Department of Chemistry, Carnegie–Mellon University, Pittsburgh, Pennsylvania 15213
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R. F. Stewart;
R. F. Stewart
Department of Chemistry, Carnegie–Mellon University, Pittsburgh, Pennsylvania 15213
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J. A. Pople
J. A. Pople
Department of Chemistry, Carnegie–Mellon University, Pittsburgh, Pennsylvania 15213
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J. Chem. Phys. 51, 2657–2664 (1969)
Article history
Received:
March 17 1969
Connected Content
A companion article has been published:
Self‐Consistent Molecular‐Orbital Methods. III. Comparison of Gaussian Expansion and PDDO Methods Using Minimal STO Basis Sets
A companion article has been published:
Self‐Consistent Molecular‐Orbital Methods. II. Projection of Diatomic Differential Overlap (PDDO)
Citation
W. J. Hehre, R. F. Stewart, J. A. Pople; Self‐Consistent Molecular‐Orbital Methods. I. Use of Gaussian Expansions of Slater‐Type Atomic Orbitals. J. Chem. Phys. 15 September 1969; 51 (6): 2657–2664. https://doi.org/10.1063/1.1672392
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