Abstract
Abstract The ability of the atomic pseudopotential proposed in Part I to reproduce the all-electron basis set extension and correlation effects in molecules has been tested on F2 and Cl2 through systematic comparisons between pseudopotential and all-electron calculations, at the SCF and CI levels, using three basis sets. The pseudopotentials monoelectronic energy levels, bond lengths and force constants have a perfect basis set dependence. The coefficients of the excited determinants in the ground-state wave-function resulting from limited CI's are in surprisingly high agreement, and the pseudopotential calculation reproduces very well the correlation effects on bond lengths and force constants, despite a 10 per cent overestimate of the total correlation energy. Pseudopotential extended (double-zeta+d) basis set calculations, including CI, have been performed on Br2 and I2, giving for I2 a better mean agreement with experiment than the presently available best all-electron calculations. The calculated dissociation energies fairly reproduce the experimental ordering (Cl2>Br2>I2>F2).
Keywords
PseudopotentialBasis setBond-dissociation energyBond lengthChemistryExcited stateElectronic correlationAtomic physicsWave functionBasis (linear algebra)Force constantDissociation (chemistry)MoleculePhysicsComputational chemistryDensity functional theoryPhysical chemistryMathematics
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Publication Info
- Year
- 1977
- Type
- article
- Volume
- 33
- Issue
- 1
- Pages
- 181-197
- Citations
- 78
- Access
- Closed
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Cite This
Ch. Teichteil,
Jean‐Paul Malrieu,
J.-C. Barthelat
(1977).
Non-empirical pseudopotentials for molecular calculations.
Molecular Physics
, 33
(1)
, 181-197.
https://doi.org/10.1080/00268977700103151
Identifiers
- DOI
- 10.1080/00268977700103151