Physical review. A, General physics · 1974 · 30 citations · 6 references
Natural SciencesChemistryPhysicsQuantum ChemistryQuantum MechanicsTheoretical ChemistryAb Initio MethodsApproximation MethodsElectron ConfigurationsElectron CorrelationMolecular Orbital TheoryTwo-body ProblemBonding In Diatomic MoleculesElectron-electron InteractionsGround State PropertiesNatural Orbital TheoryOrbital Symmetry AnalysisSelf-consistent Field ConfigurationsTwo-dimensional Electron SystemsVariational Problems
The determination of shielded diatomic orbitals (SDO) is investigated from the exact resolution, in prolate-spheroidal coordinates, of the two-center problem with an effective parametric potential. This potential, which is cylindrically symmetric in order to preserve the separability of the Schr\"odinger equation, is obtained either by classical electrostatic considerations or by a variational procedure. Calculations are carried out for two-electron diatomic systems, i.e., ${\mathrm{H}}_{2}$, $\mathrm{He}_{2}^{}{}_{}{}^{2+}$, and He${\mathrm{H}}^{+}$ in their ground state. From the results and also from theoretical considerations, these SDO appear to be close to self-consistent-field orbitals. Extension to the $N$-electron problem is considered.
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