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L. Mattioni

Publications and source records attributed to L. Mattioni.

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Long Range Bond-Bond Correlations in Dense Polymer Solutions

The scaling of the bond-bond correlation function $C(s)$ along linear polymer chains is investigated with respect to the curvilinear distance, $s$, along the flexible chain and the monomer density, $ρ$, via Monte Carlo and molecular dynamics simulations. % Surprisingly, the correlations in dense three dimensional solutions are found to decay with a power law $C(s) \sim s^{-ω}$ with $ω=3/2$ and the exponential behavior commonly assumed is clearly ruled out for long chains. % In semidilute solutions, the density dependent scaling of $C(s) \approx g^{-ω_0} (s/g)^{-ω}$ with $ω_0=2-2ν=0.824$ ($ν=0.588$ being Flory's exponent) is set by the number of monomers $g(ρ)$ contained in an excluded volume blob of size $ξ$. % Our computational findings compare well with simple scaling arguments and perturbation calculation. The power-law behavior is due to self-interactions of chains on distances $s \gg g$ caused by the connectivity of chains and the incompressibility of the melt. %

cond-mat.soft

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

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.

cond-mat.stat-mech