A Linear Response Polarizability Theory for an Extended Fano–DeVoe Model with Comments on the Joint Use of Both Short- and Long-Range Inter(sub)molecular Interaction Approximations

• Hirotoshi Ito

  Department of Materials Science, The University of Electro-Communications

• Yasumasa J I’Haya

  Department of Materials Science, The University of Electro-Communications

抄録

An approach to extend the Fano–DeVoe model is presented for copolymer systems by making use of the Green’s operator method within the dipole–dipole approximation. We derive a model Hamiltonian for a system by expanding its primitive Hamiltonian in terms of a bare complete basis set consisting of zero-order one-site and two-site excitation states in the first-order perturbation theory. A generalized extension of the Fano–DeVoe theory can be given by the polarizability tensor derived for this model Hamiltonian. As a more refined way, we derive another model Hamiltonian by expanding the primitive Hamiltonian of the system in terms of the corrected complete basis set consisting of the first-order excitation states. With such model Hamiltonians, we can fabricate polarizability theories on the same footing with the exciton wave function approaches based on the usual perturbation theory. Simplified schemes for the latter model Hamiltonians are applied to the copolymer system consisting of such chromophores that have permanent dipole moments in their ground states. Even if the constituent chromophores do not have permanent moments, extension of the Fano–DeVoe model is made by allowing for the total polymer ground state wave function corrected in terms of two-site excitation states. To circumvent the deficiency of the dipole approximation in the region of short separations of submolecules, we show a recipe as to how to make use of the monopole approximation together with the dipole approximation in conformity with the compromized idea of Moffitt.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 60 (8), 2791-2801, 1987-08-01

  Oxford University Press (OUP)

キーワード

• General Chemistry

詳細情報

• CRID: 1360565169056227200
• NII論文ID: 130001981911
• DOI: 10.1246/bcsj.60.2791
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/60/8/2791/55725420/bcsj.60.2791.pdf
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