Computational Chemistry and Molecular Modeling
Atomic, Molecular and Optical Physics
Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
Recent Xα 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 Xα dissociation energies overestimate the experimental values by almost 2 eV. Therefore, we have examined several refinements of the Xα theory and their effects on molecular bond lengths, bond energies, and vibrational frequencies. Among them, gradient corrections to the Xα 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 Xα approximation.
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