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Dielectric disperison of linear polyelectrolytes
Author(s) -
Michael Schurr J.
Publication year - 1971
Publication title -
biopolymers
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.556
H-Index - 125
eISSN - 1097-0282
pISSN - 0006-3525
DOI - 10.1002/bip.360100810
Subject(s) - chemistry , counterion , dielectric , diffusion , ion , relaxation (psychology) , chemical physics , polyelectrolyte , thermodynamics , thermal conduction , condensed matter physics , statistical physics , physics , quantum mechanics , polymer , organic chemistry , social psychology , psychology
A three‐dimensional (gaussian) model is formulated that permits evaluation of the one‐dimensional fourier cosine transform of the counterion‐counterion coulombic interaction energy ϕ k . It is shown that ϕ k is much larger for small k than was assumed by Oosawa; consequently, the magnitude of his dielectric increment, and also his relaxation time, must be drastically revised to smaller values. Evidently, the self‐field of the fluctuation is large enough to seriously depress the amplitude of the spontaneous fluctuations, and to force Ohmic conduction of the ions at a rate far in excess of the rate of translational diffusion. Finally, it is noted that in highly conducting bulk solvents, where both positive and negative counterfoils coexist in the ion‐atmosphere, one might expect to observe a low‐frequency component of the dielectric relaxation arising from unequal rates of diffusion of the positive and negative species, in analogy with the situation for spherical colloidal particles. In such a circumstance, the basic counterfoil fluctuation mechanism proposed by Oosawa would acquire a new validity.