Li Cuilian, Ma H R
Institute of Theoretical Physics, Shanghai Jiao Tong University, Shanghai 200240, People's Republic of China.
J Chem Phys. 2004 Jul 22;121(4):1917-27. doi: 10.1063/1.1767155.
By using the field-theoretic method, we established a unified systematic formulation of a model of counterions and coions confined in two similarly charged plates, and calculated the density distributions of counterions and coions with various coupling parameters by the two methods: Poisson-Boltzmann (PB) approach and the strong coupling (SC) theory, respectively. We also performed Monte Carlo simulations, and obtained the density distributions of counterions and coions with several different coupling parameters. Comparing our theoretical results with those from Monte Carlo simulation, we find that the PB approach is valid when the coupling parameter Xi is smaller than 1, but, as Xi > or = 1, the results by the PB approach deviate from the corresponding Monte Carlo simulation data, and the deviation gets larger with the coupling parameter increasing. This shows that the PB approach is completely invalid when the coupling parameter is equal to 1 or larger than 1. For the latter case, the development trend of the distribution curve calculated by SC theory agrees with that from Monte Carlo simulation as the coupling parameter increases. This demonstrates that the SC theory can give a qualitative available explanation on the density distribution of the counterions in the system in which the coupling parameters are strictly confined.
通过使用场论方法,我们建立了一个统一的系统公式,用于描述限制在两个带相同电荷平板之间的反离子和同离子模型,并分别用两种方法计算了具有不同耦合参数的反离子和同离子的密度分布:泊松 - 玻尔兹曼(PB)方法和强耦合(SC)理论。我们还进行了蒙特卡罗模拟,并获得了具有几个不同耦合参数的反离子和同离子的密度分布。将我们的理论结果与蒙特卡罗模拟结果进行比较,我们发现当耦合参数Xi小于1时,PB方法是有效的,但是,当Xi≥1时,PB方法的结果偏离了相应的蒙特卡罗模拟数据,并且随着耦合参数的增加偏差变得更大。这表明当耦合参数等于1或大于1时,PB方法完全无效。对于后一种情况,随着耦合参数增加,由SC理论计算的分布曲线的发展趋势与蒙特卡罗模拟结果一致。这表明SC理论可以对耦合参数受到严格限制的系统中反离子的密度分布给出定性的有效解释。