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Long-range correlations in a polymer chain due to its connectivity

Publication ,  Journal Article
Shirvanyants, D; Panyukov, S; Liao, Q; Rubinstein, M
Published in: Macromolecules
2008

The analysis of intrachain monomeric interactions reveals a new effect in the description of polymer conformations in dilute theta-solutions, semidilute solutions, and melts. The chain connectivity modifies the effective monomeric interaction, which results in the long range correlations between orientations of polymer bonds, that decay as a power law. A major modification of the standard polymer models was made to describe this effect. We predict the power-law decay of the bond-vector correlation function of a polymer in the theta-solvent, \textless a(i)a(j)\textgreater similar to vertical bar i-j vertical bar(-3/2), (a(i) is the ith bond vector) instead of commonly assumed exponential decay. We calculated the length dependence of the ratio of the mean squared size of a chain segment to its length s. Our theory predicts that this ratio has a maximum below the theta-point due to the balance of the new effective interaction and the two-body attraction. The Flory characteristic ratio C-n of a chain with n main chain bonds is found to approach its asymptotic value C-infinity as n(-1/2) and not as n(-1), predicted by the classical polymer models. We show that the necessary conditions for the existence of new effective interactions is the chain connectivity and nonzero range of monomeric interactions.

Duke Scholars

Published In

Macromolecules

DOI

ISSN

0024-9297

Publication Date

2008

Related Subject Headings

  • Polymers
  • 09 Engineering
  • 03 Chemical Sciences
 

Citation

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Shirvanyants, D., Panyukov, S., Liao, Q., & Rubinstein, M. (2008). Long-range correlations in a polymer chain due to its connectivity. Macromolecules. https://doi.org/10.1021/ma071443r
Shirvanyants, David, Sergey Panyukov, Qi Liao, and Michael Rubinstein. “Long-range correlations in a polymer chain due to its connectivity.” Macromolecules, 2008. https://doi.org/10.1021/ma071443r.
Shirvanyants D, Panyukov S, Liao Q, Rubinstein M. Long-range correlations in a polymer chain due to its connectivity. Macromolecules. 2008;
Shirvanyants, David, et al. “Long-range correlations in a polymer chain due to its connectivity.” Macromolecules, 2008. Manual, doi:10.1021/ma071443r.
Shirvanyants D, Panyukov S, Liao Q, Rubinstein M. Long-range correlations in a polymer chain due to its connectivity. Macromolecules. 2008;
Journal cover image

Published In

Macromolecules

DOI

ISSN

0024-9297

Publication Date

2008

Related Subject Headings

  • Polymers
  • 09 Engineering
  • 03 Chemical Sciences