Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, Wageningen 6703HB, The Netherlands.
J Chem Phys. 2009 Dec 28;131(24):244115. doi: 10.1063/1.3276286.
A hybrid modeling approach is proposed for inhomogeneous polymer solutions. The method is illustrated for the depletion problem with polymer chains up to N=10(3) segments in semidilute solutions and good solvent conditions. In a three-dimensional volume, a set of freely jointed chains is considered for which the translational degrees of freedom are sampled using a coarse grained Monte Carlo simulation and the conformational degrees of freedom of the chains are computed using a modified self-consistent field theory. As a result, both intramolecular and intermolecular excluded volume effects are accounted for, not only for chains near the surface, but in the bulk as well. Results are consistent with computer simulations and scaling considerations. More specifically, the depletion thickness, which is a measure for the bulk correlation length, scales as delta proportional to phi(-0.75) and converges to the mean field result in the concentrated regime.
提出了一种用于非均匀聚合物溶液的混合建模方法。该方法针对聚合物链在半浓溶液和良溶剂条件下达到 N=10(3)段的耗竭问题进行了说明。在三维体积中，考虑了一组自由连接链，其平移自由度使用粗粒蒙特卡罗模拟进行采样，链的构象自由度使用改进的自洽场理论进行计算。结果，不仅考虑了表面附近的链，还考虑了分子内和分子间的排斥体积效应。结果与计算机模拟和标度考虑一致。更具体地说，耗竭厚度是衡量体相关长度的一个指标，其标度为 delta 正比于 phi(-0.75)，并在浓缩状态下收敛到平均场结果。
