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Geminal Localization in the Separatedhyphen;Pair pgr;hyphen;Electronic Model of Benzene

机译:Geminal Localization in the Separatedhyphen;Pair pgr;hyphen;Electronic Model of Benzene

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摘要

A problem of the geminal ``localization'' in the separatedhyphen;pairpgr;hyphen;electronic model of benzene is studied for a wide range of a coupling constant using the Parisermdash;Parrmdash;Poplehyphen;type Hamiltonian. The general form of the ``localized geminals'' leading to the separatedhyphen;pair wavefunction of theC3hsymmetry is found as a function of two free parameters. These geminals are used in the separatedhyphen;pair model calculation, showing that the previously used localization corresponding to the equivalent orbitals (i.e., the localized Hartreemdash;Fock orbitals) is not the best one from the separatedhyphen;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 theD6hpoint group. Finally, the general implications of the ``symmetry dilemma'' are briefly discussed for both independenthyphen;particle and separatedhyphen;pair models.

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