Hoda Nazish, Kumar Satish
Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455, USA.
Phys Rev E Stat Nonlin Soft Matter Phys. 2009 Feb;79(2 Pt 1):020801. doi: 10.1103/PhysRevE.79.020801. Epub 2009 Feb 3.
Brownian dynamics simulations with hydrodynamic interaction (HI) are performed to study the effect of chain length on the diffusion of a polymer chain adsorbed onto flat surfaces. Bead-rod as well as bead-spring chains, with Hookean and finitely extensible nonlinear elastic (FENE) springs, are used to model the polymer chain, and the no-slip boundary condition for the solvent is incorporated exactly. Simulations for short chains (N<or=100) predict that the translational diffusivity in the planar direction D{ parallel} approximately N;{-nu} , where N is the chain length, with nu approximately 0.75 for bead-rod chains and bead-spring chains connected by stiff FENE springs and nu approximately 1 for bead-spring chains connected by flexible FENE and Hookean springs. We find that near chemically homogeneous surfaces, the scaling exponent nu depends upon three factors: chain flexibility, strength of HI, and solvent quality. The nu value changes from 0.75 to 1 with either an increase in chain flexibility, a decrease in the strength of HI, or a decrease in solvent quality. However, near a chemically heterogeneous surface, nu is always 1.
进行了包含流体动力学相互作用(HI)的布朗动力学模拟,以研究链长对吸附在平面上的聚合物链扩散的影响。采用珠-棒链以及珠-弹簧链,分别使用胡克弹簧和有限可拉伸非线性弹性(FENE)弹簧来模拟聚合物链,并精确纳入了溶剂的无滑移边界条件。对短链(N≤100)的模拟预测,平面方向上的平动扩散系数D∥约为N-ν,其中N为链长,对于由刚性FENE弹簧连接的珠-棒链和珠-弹簧链,ν约为0.75,而对于由柔性FENE弹簧和胡克弹簧连接的珠-弹簧链,ν约为1。我们发现,在化学性质均匀的表面附近,标度指数ν取决于三个因素:链的柔性、HI的强度和溶剂质量。随着链柔性的增加、HI强度的降低或溶剂质量的降低,ν值从0.75变为1。然而,在化学性质不均匀的表面附近,ν始终为1。