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Dynamical Properties of the Slithering Snake Algorithm: A numerical test of the activated reptation hypothesis

L. Mattioni·J. P. Wittmer·J. Baschnagel·J. -L. Barrat·E. Luijten
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Abstract

The correlations in the motion of reptating polymers in their melt are investigated by means of kinetic Monte Carlo simulations of the three dimensional slithering snake version of the bond-fluctuation model. Surprisingly, the slithering snake dynamics becomes inconsistent with classical reptation predictions at high chain overlap (either chain length $N$ or volume fraction $ϕ$) where the relaxation times increase much faster than expected. This is due to the anomalous curvilinear diffusion in a finite time window whose upper bound $τ_+$ is set by the chain end density $ϕ/N$. Density fluctuations created by passing chain ends allow a reference polymer to break out of the local cage of immobile obstacles created by neighboring chains. The dynamics of dense solutions of snakes at $t \ll τ_+$ is identical to that of a benchmark system where all but one chain are frozen. We demonstrate that it is the slow creeping of a chain out of its correlation hole which causes the subdiffusive dynamical regime. Our results are in good qualitative agreement with the activated reptation scheme proposed recently by Semenov and Rubinstein [Eur. Phys. J. B, {\bf 1} (1998) 87]. Additionally, we briefly comment on the relevance of local relaxation pathways within a slithering snake scheme. Our preliminary results suggest that a judicious choice of the ratio of local to slithering snake moves is crucial to equilibrate a melt of long chains efficiently.

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L. Mattioni, J. P. Wittmer, J. Baschnagel, J. -L. Barrat, E. Luijten. 2003-03-22. Dynamical Properties of the Slithering Snake Algorithm: A numerical test of the activated reptation hypothesis. https://doi.org/10.1140/epje%2Fi2002-10122-1

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