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  • 1985-1989  (4)
  • 1986  (4)
Material
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  • 1985-1989  (4)
Year
  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 19 (1986), S. 2770-2778 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 3007-3022 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We introduce a lattice spin field theory which formally provides an exact description of the statistics of nonoverlapping, nonintersecting rods on regular lattices. The theory is applicable to arbitrary rod length distributions and arbitrary volume fractions. The mean field approximation reproduces Flory–Huggins theory for rods on a strict lattice, but our theory permits the rigorous and systematic evaluation of corrections to the mean field entropies. We present those corrections as a cluster expansion for the entropy density which involves a double expansion in powers of the volume fraction ψ and the inverse of the lattice coordination number z−1. Our results are compared for specific cases with those of DiMarzio's theory which is more accurate than mean field. For dimers which are equally distributed among the possible lattice directions of a hypercubic lattice, we find very good agreement between our theory and DiMarzio's with ours giving a slightly larger entropy density when corrections to mean field to order ψ4 are included. Through order ψ3, our entropy for longer rods is identical to that of DiMarzio's expanded similarly. Our dimer results, however, demonstrate that the ψ4 term for rods contains contributions which we attribute to locally ordered configurations and which are absent in DiMarzio's theory. Our results are compared with the exact entropy density for dimers fully covering an infinite square planar lattice; the inclusion of corrections to mean field up to order z−2 narrows the error from 33.8% for mean field to 7.85%. Our theory, however, also describes the dimer–monomer problem which has not been very amenable to analytic theories.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 7036-7047 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We continue the analysis of the lattice spin-field theory which is introduced in paper I and which formally gives the exact entropy for a set of completely flexible self-avoiding polymers on a lattice. The model allows for arbitrary chain length distributions and arbitrary polymer volume fractions. Use of random fields produces a field theory from which Flory–Huggins results are recovered in the mean field limit. Here we recast the mean field formulation to allow for the rigorous and systematic evaluation of corrections by means of a cluster expansion. We then calculate corrections to the mean field directly up to fourth order and provide a systematic diagrammatic method for evaluating general order corrections. Our results illustrate the polymer concentration dependence of the corrections to the Flory–Huggins mean field results as well as provide the origins for the entropic contribution to the Flory χ parameter and its concentration dependence. Generalizations to treat rods and semiflexible polymers will be given elsewhere.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 449-464 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A theoretical description of excluded volume in polyelectrolytes is considered in the flexible chain limit. The approach generalizes the work of Kholodenko and Freed and removes some deficiencies, present in their work, which become apparent in further extensions of the theory. Renormalization group calculations are pursued to order ε=4−d for the mean square end-to-end distance 〈R2〉, the radius of gyration 〈S2〉, and the second virial coefficient A2. The importance of including both a short range excluded volume interaction as well as a long range electrostatic one is stressed. The electrostatic interaction is effectively treated as a perturbation, so that the results are valid only in the weak electrostatic coupling region. The theory shows that polyelectrolyte excluded volume effects cannot generally be described in a scaling limit, and generalized scaling laws are derived which contain several parameters including the two interaction parameters. A qualitative comparison of the theory with available experimental data is included, and a program for evaluating effective charge distributions on polyelectrolytes is proposed based upon comparison of experiments with extensions of the theory to higher concentrations.
    Type of Medium: Electronic Resource
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