Departamento de Engenharia Mecânica, Faculdade de Tecnologia, Universidade de Brasília, Campus Universitário Darcy Ribeiro, Brasília-DF, Brazil.
J Chem Phys. 2011 Jun 28;134(24):244903. doi: 10.1063/1.3604813.
In our recent work on concentrated suspensions of uniformly porous colloidal spheres with excluded volume interactions, a variety of short-time dynamic properties were calculated, except for the rotational self-diffusion coefficient. This missing quantity is included in the present paper. Using a precise hydrodynamic force multipole simulation method, the rotational self-diffusion coefficient is evaluated for concentrated suspensions of permeable particles. Results are presented for particle volume fractions up to 45% and for a wide range of permeability values. From the simulation results and earlier results for the first-order virial coefficient, we find that the rotational self-diffusion coefficient of permeable spheres can be scaled to the corresponding coefficient of impermeable particles of the same size. We also show that a similar scaling applies to the translational self-diffusion coefficient considered earlier. From the scaling relations, accurate analytic approximations for the rotational and translational self-diffusion coefficients in concentrated systems are obtained, useful to the experimental analysis of permeable-particle diffusion. The simulation results for rotational diffusion of permeable particles are used to show that a generalized Stokes-Einstein-Debye relation between rotational self-diffusion coefficient and high-frequency viscosity is not satisfied.
在我们最近关于具有排斥体积相互作用的均匀多孔胶体球的浓缩悬浮液的研究中,计算了各种短时间动力学性质,除了旋转自扩散系数。本文包括了这个缺失的量。我们使用精确的流体动力多极模拟方法,评估了可渗透粒子的浓缩悬浮液的旋转自扩散系数。结果显示的粒子体积分数高达 45%,以及广泛的渗透率值。从模拟结果和早期的一阶维里系数结果,我们发现可渗透球体的旋转自扩散系数可以被缩放为相同大小的不可渗透粒子的相应系数。我们还表明,先前考虑的平移自扩散系数也适用类似的缩放关系。从这些缩放关系中,我们得到了浓缩体系中旋转和平移自扩散系数的精确解析近似,这对可渗透粒子扩散的实验分析很有用。可渗透粒子旋转扩散的模拟结果表明,旋转自扩散系数与高频粘度之间的广义斯托克斯-爱因斯坦-德拜关系不成立。