We have performed simulations of the model of infinitely thin rigid rods undergoing rotational and translational diffusion, subject to the restriction that no two rods can cross one another, for various concentrations well into the semidilute regime. We used a modification of the algorithm of Doi et al [J. Phys. Soc. Jpn. 53, 3000 (1984)] that simulates diffusive dynamics using a Monte Carlo method and a nonzero time step. In the limit of zero time step, this algorithm is an exact description of diffusive dynamics subject to the noncrossing restriction. For a wide range of concentrations in the semidilute regime, we report values of the long time rotational diffusion constant of the rods, extrapolated to the limit of zero time step, for various sets of values of the infinite dilution (bare) diffusion constants. These results are compared with the results of a previous simulation of the model by Doi et al. and of previous simulations of rods with finite aspect ratio by Fixman and by Cobb and Butler that had been extrapolated to the limit of infinitely thin rods. The predictions of the Doi-Edwards (DE) scaling law do not hold for this model for the concentrations studied. The simulation data for the model display two deviations from the predictions of the DE theory that have been observed in experimental systems in the semidilute regime, namely, the very slow approach toward DE scaling behavior as the concentration is increased and the large value of the prefactor in the DE scaling law. We present a modified scaling principle for this model that is consistent with the simulation results for a broad range of concentrations in the semidilute regime. The modified scaling principle takes into account two physical effects, which we call “leakage” and “drift,” that were found to be important for the transport properties of a simpler model of nonrotating rods on a lattice [Y.-L. S. Tse and H. C. Andersen, J. Chem. Phys. 136, 024904 (2012)].
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Research Article| July 24 2013
Modified scaling principle for rotational relaxation in a model for suspensions of rigid rods
Ying-Lung Steve Tse;
Ying-Lung Steve Tse, Hans C. Andersen; Modified scaling principle for rotational relaxation in a model for suspensions of rigid rods. J. Chem. Phys. 28 July 2013; 139 (4): 044905. https://doi.org/10.1063/1.4816001
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