2007
DOI: 10.1103/physrevlett.98.128303
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Confined Space and Effective Interactions of Multiple Self-Avoiding Chains

Abstract: We study the link between three seeming-disparate cases of self-avoiding polymers: strongly overlapping multiple chains in dilute solution, chains under spherical confinement, and the onset of semidilute solutions. Our main result is that the free energy for overlapping n chains is independent of chain length and scales as n9/4, slowly crossing over to n3, as n increases. For strongly confined polymers inside a spherical cavity, we show that rearranging the chains does not cost an additional free energy. Our r… Show more

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Cited by 71 publications
(127 citation statements)
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“…As the two chains can gain conformational entropy by demixing, they effectively repel each other. Note that the free energy cost for simultaneous overlap of n chains scales as n 9/4 in the dilute regime and then increases faster as n 3 in the more concentrated regime, independent of the chain length [15,16]. Thus, for two intermingling chains illustrated in Fig.…”
Section: Theorymentioning
confidence: 96%
“…As the two chains can gain conformational entropy by demixing, they effectively repel each other. Note that the free energy cost for simultaneous overlap of n chains scales as n 9/4 in the dilute regime and then increases faster as n 3 in the more concentrated regime, independent of the chain length [15,16]. Thus, for two intermingling chains illustrated in Fig.…”
Section: Theorymentioning
confidence: 96%
“…These results need to be appended by a proper account of excluded volume effect in order to compare with experimental systems. Even for an isolated spherical cavity, there is a continuing debate [46][47][48] for the form of the confinement free energy. However, when the excluded volume effect is removed, our exact results must be recovered.…”
Section: ͑42͒mentioning
confidence: 99%
“…For λ ≥ 1, the total free energy is independent of l, therefore, there is no force driving segregation and the motion of the two chains is purely diffusive [18]. For λ ≤ 1, F (l) is a monotonically increasing function of l, and this repulsive potential drives segregation [19].…”
mentioning
confidence: 99%
“…For a single chain confined in a rectangular box, assuming homogeneous distribution of monomers [16,17,18], leads to…”
mentioning
confidence: 99%
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