Abstract
A problem of the geminal ``localization'' in the separated-pair π-electronic model of benzene is studied for a wide range of a coupling constant using the Pariser—Parr—Pople-type Hamiltonian. The general form of the ``localized geminals'' leading to the separated-pair wavefunction of the C3h symmetry is found as a function of two free parameters. These geminals are used in the separated-pair model calculation, showing that the previously used localization corresponding to the equivalent orbitals (i.e., the localized Hartree—Fock orbitals) is not the best one from the separated-pair model viewpoint, except for vanishingly small coupling constants. The optimization is also carried out after the projection of the single antisymmetrized product of geminals function onto the totally symmetric subspace of the D6h point group. Finally, the general implications of the ``symmetry dilemma'' are briefly discussed for both independent-particle and separated-pair models.
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