接枝聚电解质的蒙特卡罗模拟与分子理论

Monte Carlo simulation and molecular theory of tethered polyelectrolytes.

作者信息

Hehmeyer Owen J, Arya Gaurav, Panagiotopoulos Athanassios Z, Szleifer Igal

机构信息

Department of Chemical Engineering, Princeton University, Princeton, New Jersey 08544, USA.

出版信息

J Chem Phys. 2007 Jun 28;126(24):244902. doi: 10.1063/1.2747600.

Abstract

We investigate the structure of end-tethered polyelectrolytes using Monte Carlo simulations and molecular theory. In the Monte Carlo calculations we explicitly take into account counterions and polymer configurations and calculate electrostatic interaction using Ewald summation. Rosenbluth biasing, distance biasing, and the use of a lattice are all used to speed up Monte Carlo calculation, enabling the efficient simulation of the polyelectrolyte layer. The molecular theory explicitly incorporates the chain conformations and the possibility of counterion condensation. Using both Monte Carlo simulation and theory, we examine the effect of grafting density, surface charge density, charge strength, and polymer chain length on the distribution of the polyelectrolyte monomers and counterions. For all grafting densities examined, a sharp decrease in brush height is observed in the strongly charged regime using both Monte Carlo simulation and theory. The decrease in layer thickness is due to counterion condensation within the layer. The height of the polymer layer increases slightly upon charging the grafting surface. The molecular theory describes the structure of the polyelectrolyte layer well in all the different regimes that we have studied.

摘要

我们使用蒙特卡罗模拟和分子理论研究了末端连接的聚电解质的结构。在蒙特卡罗计算中,我们明确考虑了抗衡离子和聚合物构型,并使用埃瓦尔德求和计算静电相互作用。罗森布鲁斯偏差、距离偏差和晶格的使用都被用来加速蒙特卡罗计算,从而能够对聚电解质层进行高效模拟。分子理论明确纳入了链构象和抗衡离子凝聚的可能性。通过蒙特卡罗模拟和理论,我们研究了接枝密度、表面电荷密度、电荷强度和聚合物链长度对聚电解质单体和抗衡离子分布的影响。对于所有研究的接枝密度,使用蒙特卡罗模拟和理论均观察到在强电荷区域刷高急剧下降。层厚度的减小是由于层内抗衡离子的凝聚。对接枝表面充电后,聚合物层的高度略有增加。分子理论在我们研究的所有不同区域中都很好地描述了聚电解质层的结构。

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