Abstract
The use of numerical solutions to atomlike single site potentials as a basis for molecular orbital calculations is investigated. The atomic Hamiltonian is modified by addition of a potential well to induce additional discrete levels with the desired spatial characteristics. The discrete variational method is employed, in the Hartree-Fock-Slater model, to compare levels obtained for FeCl4 using multiple-scattering, conventional Slater-orbital, and numerical basis sets. The numerical technique is shown to be an accurate and efficient method for treating general (non-muffin-tin) molecular potentials. The errors in energy levels due to the muffin-tin approximation are calculated.
Keywords
Basis setHamiltonian (control theory)Basis (linear algebra)Molecular orbitalScatteringQuantum mechanicsHartree–Fock methodPhysicsComputational chemistryMathematicsStatistical physicsChemistryMoleculeGeometryMathematical optimization
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Publication Info
- Year
- 1973
- Type
- article
- Volume
- 59
- Issue
- 12
- Pages
- 6412-6418
- Citations
- 400
- Access
- Closed
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Cite This
F. W. Averill,
D. E. Ellis
(1973).
An efficient numerical multicenter basis set for molecular orbital calculations: Application to FeCl4.
The Journal of Chemical Physics
, 59
(12)
, 6412-6418.
https://doi.org/10.1063/1.1680020
Identifiers
- DOI
- 10.1063/1.1680020