Bulk properties from finite-cluster calculations. VI. A finite-size perturbation theory for the Hartree–Fock energy of linear oligomers

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Abstract
A finite-size perturbation theory that expresses the total Hartree–Fock energy and the orbital energies of a finite nonmetallic linear oligomer composed of N identical unit cells as power series in ν=N−1 is derived. The coefficients for the first three terms of these series are evaluated explicitly through the first order of the Hartree–Fock formalism. The form of the uncoupled second-order contributions is discussed. The resulting expressions contain infinite sums involving the Wannier orbitals of the bulk polymer. The presence of nonanalytic terms in the expansion is also commented upon.