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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and experimental chemistry 10 (1976), S. 595-600 
    ISSN: 1573-935X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and experimental chemistry 10 (1976), S. 587-594 
    ISSN: 1573-935X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Conclusions The technique used above for calculating electronic excitations is equivalent to the random phase approximation, but permits a clearer understanding of the approximations made. The linearization with respect to Ø in the derivation of the equations for the excited states means that the approximation made is valid only for small changes in the spin (or electron) density in the atoms in the excited states from that in the ground state. This is always the case for fairly small excitation energies. The proposed calculation technique may be used to calculate excitations both in long conjugated molecules and in ordinary molecules just as well as the Pariser-Parr-Pople and random phase approximations [14, 17, 18]. We note that another approach was used in [6] to find the energy of the first triplet level in polyenes. In that paper the wave function of the generalized Hartree-Fock approximation was projected onto a singlet (ground) and a triplet state. The latter was treated as a very low triplet excited state. However, as shown in [1, 2], the energies of these (the singlet and triplet) states differ by a quantity that decreases like N−2 or even faster as N→∞. On the other hand, as shown in [7], the energy of the first triplet excitation should decrease like Ω1 ∼ 1/N as N→∞. This implies that the interaction between electrons above the generalized Hartree-Fock approximation must be taken into account in order to obtain the first triplet state.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1573-935X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Conclusions The variation procedure presented above is equivalent to the summation of only zero-audio diagrams. However, arguments exist based on the theory of perturbation with a small interaction, according to which calculation of the second (superconducting) channel and, consequently, consideration of diagrams of a broader (parquet) class [12] are necessary. The basis for the restrictions accepted by us is first, that we are not examining a small interaction and second, the presence of long-range coulombic repulsion of electrons evidently makes optional the consideration of the superconducting channel even at small γmn. Recently it was shown in [13] that for the case of a one-dimensional problem with attraction the accurate spectrum of Fermi excitations coincides in form with the spectrum obtained on the basis of the Bardeen-Cooper-Schrieffer (BCS) approximation and that the slit in the accurate spectrum of a one-dimensional superconductor differs from the BCS slit only in the pre-exponential factor, which makes it possible to look forward to the production of an accurate excitation spectrum in a self-consistent procedure. It should also be noted that the wave function (3)–(5) for the case of SW is not an eigenfunction of the square of the total spin operator Ŝ2 and it is not an eigenfunction of the total pulse operator $$\hat P$$ of the system of electrons for the case of CW. After projecting to a state with accurate quantum numbers (S=0 for SW states and P=0 for CW states) a new function is obtained, which as previously depends on one variation parameter δ. In this case the new value of δ agrees with the old value with an accuracy to terms ∼1/N. All characteristics of the system calculated with the new and old variation functions including total energy of the excitation spectrum, etc., coincide with this accuracy. Exceptions are spin density, which is equal to zero on each atom of the chain for a singlet component of the SW state [3, 14], and electron density, which is equal to one on each atom of the chain for components with P=0 of the CW state, so that the charge on each atom is equal to zero. Thus, “spin waves” or “charge waves” as such do not exist in the states of type SW or CW with accurate variation functions and only the corresponding correlation functions indicate directly an antiferromagnetic spin structure [3] or a ferroelectric phase.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and experimental chemistry 12 (1977), S. 457-462 
    ISSN: 1573-935X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and experimental chemistry 12 (1976), S. 563-569 
    ISSN: 1573-935X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and experimental chemistry 13 (1977), S. 115-120 
    ISSN: 1573-935X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 9 (1975), S. 605-625 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electronic structure and collective excitations of long molecules with conjugated bonds in the main chain (linear polyene, cyclic polyene, polyphenylacetylene (PPA)) are considered. The electronic structure of these polymers is investigated by the generalized Hartree-Fock method. The first triplet collective excitations are derived using the compact technique of the Green's functions. This approach is shown to be equivalent to the random phase approximation. The problem of the triplet collective excitations in long cyclic polyenes is solved analytically and good agreement with the exact results is found. The effects of the free ends in a linear polyene are considered. The approach developed for PPA and polyene may be applied to an investigation of any polymer molecule with equivalent unit cells.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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