Abstract
Abstract Recent X α calculations of bond energies and other related properties of first‐row diatomic molecules show very encouraging agreement with experiment. In the worst cases, however, the X α dissociation energies overestimate the experimental values by almost 2 eV. Therefore, we have examined several refinements of the X α theory and their effects on molecular bond lengths, bond energies, and vibrational frequencies. Among them, gradient corrections to the X α exchange energy and also some variations of the local spin‐density correlation energy approximation are considered. We find that a local exchange‐correlation functional with gradient corrections gives dissociation energies in significantly better agreement with experiment than the X α approximation.
Keywords
Diatomic moleculeDissociation (chemistry)Bond-dissociation energyAtomic physicsBond lengthChemistryMoleculeBond energyCorrelationPhysicsMolecular physicsQuantum mechanicsPhysical chemistryMathematicsGeometry
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Publication Info
- Year
- 1985
- Type
- article
- Volume
- 27
- Issue
- 5
- Pages
- 585-594
- Citations
- 65
- Access
- Closed
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Cite This
Axel D. Becke
(1985).
Local exchange‐correlation approximations and first‐row molecular dissociation energies.
International Journal of Quantum Chemistry
, 27
(5)
, 585-594.
https://doi.org/10.1002/qua.560270507
Identifiers
- DOI
- 10.1002/qua.560270507