Abstract.
Following the Flory ideality hypothesis intrachain and interchain excluded-volume interactions are supposed to compensate each other in dense polymer systems. Multichain effects should thus be neglected and polymer conformations may be understood from simple phantom chain models. Here we provide evidence against this phantom chain, mean-field picture. We analyze numerically and theoretically the static correlation function of the Rouse modes. Our numerical results are obtained from computer simulations of two coarse-grained polymer models for which the strength of the monomer repulsion can be varied, from full excluded volume (“hard monomers”) to no excluded volume (“phantom chains”). For nonvanishing excluded volume we find the simulated correlation function of the Rouse modes to deviate markedly from the predictions of phantom chain models. This demonstrates that there are nonnegligible correlations along the chains in a melt. These correlations can be taken into account by perturbation theory. Our simulation results are in good agreement with these new theoretical predictions.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
P.E. Rouse, J. Chem. Phys. 21, 1272 (1953).
M. Doi, S.F. Edwards, The Theory of Polymer Dynamics (Oxford University Press, Oxford, 1986).
M. Rubinstein, R.H. Colby, Polymer Physics (Oxford University Press, Oxford, 2003).
T.C.B. McLeish, Adv. Phys. 51, 1379 (2002).
W. Paul, G.D. Smith, Rep. Prog. Phys. 67, 1117 (2004).
L. Harnau, R.G. Winkler, P. Reineker, Europhys. Lett. 45, 488 (1999).
S. Krushev, W. Paul, G.D. Smith, Macromolecules 35, 4198 (2002).
M. Bulacu, E. van der Giessen, J. Chem. Phys. 123, 114901 (2005).
T. Kreer, J. Baschnagel, M. Müller, K. Binder, Macromolecules 34, 1105 (2001).
D. Molin, A. Barbieri, D. Leporini, J. Phys.: Condens. Matter 18, 7543 (2006).
D. Richter, J. Chem. Phys. 111, 6107 (1999).
A. Arbe, Macromolecules 34, 1281 (2001).
G. Allegra, F. Ganazzoli, in Advances in Chemical Physics, Vol. 75 (Wiley, New York, 1989) Chapt. Chain configurations and dynamics in the Gaussian approximation, pp. 265--348.
P.J. Flory, Statistical Mechanics of Chain Molecules (Wiley, New York, 1969).
J.P. Wittmer, Phys. Rev. Lett. 93, 147801 (2004).
J.P. Wittmer, Phys. Rev. E 76, 011803 (2007).
J.P. Wittmer, Europhys. Lett. 77, 56003 (2007).
P. Beckrich, Macromolecules 40, 3805 (2007).
A.N. Semenov, S.P. Obukhov, J. Phys.: Condens. Matter 17, S1747 (2005).
J. Baschnagel, J.P. Wittmer, H. Meyer, in Computational Soft Matter: From Synthetic Polymers to Proteins, edited by N. Attig, K. Binder, H. Grubmüller, K. Kremer, Vol. 23 (NIC Series, Jülich, 2004) pp. 83--140 (available from http://www.fz-juelich.de/nic-series).
J.P. Wittmer, Intrachain orientational correlations in dense polymer solutions (preprint).
H. Meyer, F. Müller-Plathe, J. Chem. Phys. 115, 7807 (2001).
H. Meyer, F. Müller-Plathe, Macromolecules 35, 1241 (2002).
T. Vettorel, H. Meyer, J. Chem. Theory Comput. 2, 616 (2006).
T. Vettorel, H. Meyer, J. Baschnagel, M. Fuchs, Phys. Rev. E 75, 041801 (2007).
K. Kremer, G.S. Grest, J. Chem. Phys. 92, 5057 (1990).
R. Auhl, J. Chem. Phys. 119, 12718 (2003).
M.P. Allen, D.J. Tildesley, Computer Simulation of Liquids (Clarendon Press, Oxford, 1987).
H.-P. Deutsch, K. Binder, J. Chem. Phys. 94, 2294 (1991).
W. Paul, J. Phys. II 1, 37 (1991).
D.P. Landau, K. Binder, A Guide to Monte Carlo Simulations in Statistical Physics (Cambridge University Press, Cambridge, 2000).
P.H. Verdier, J. Chem. Phys. 45, 2118 (1966).
S.F. Edwards, J. Phys. A: Math. Gen. 8, 1670 (1975).
A.N. Semenov, A. Johner, Eur. Phys. J. E 12, 469 (2003).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Meyer, H., Wittmer, J.P., Kreer, T. et al. Static Rouse modes and related quantities: Corrections to chain ideality in polymer melts. Eur. Phys. J. E 26, 25–33 (2008). https://doi.org/10.1140/epje/i2007-10250-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1140/epje/i2007-10250-0