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电解质离散模型中的临界性、三临界性和结晶

Criticality, tricriticality, and crystallization in discretized models of electrolytes.

作者信息

Ciach A, Stell G

机构信息

Institute of Physical Chemistry, Polish Academy of Sciences 01-224 Warszawa, Poland.

出版信息

Phys Rev E Stat Nonlin Soft Matter Phys. 2004;70(1 Pt 2):016114. doi: 10.1103/PhysRevE.70.016114. Epub 2004 Jul 15.

Abstract

The Restricted Primitive Model of ionic systems is studied within a field-theoretic approach in order to provide a theoretic basis for the qualitative difference in the phase diagrams obtained in simulations for sigma/a=1,sigma/a=2, and sigma/a>/=3 ( a is the lattice constant and sigma is the ion diameter). The evolution of the phase diagrams from the case sigma/a=1 to the case sigma/a=square root[2] [nearest-neighbor ( NN ) occupancy excluded] is studied in the model with NN repulsion, 0</=J</= infinity, supplementing Coulomb forces. The boundary of stability of the charge-disordered phase with respect to short-wavelength charge fluctuations and the tricritical point are found in a mean-field ( MF ) approximation. Next, the effect of fluctuations is studied and we find that for J exceeding a particular value J0 a fluctuation-induced first-order phase transition should be expected instead of the continuous transition found in MF. At J= J0 the line of continuous transitions splits into two lines enclosing the two-phase region, whose thickness increases from zero when J>/= J0 increases. We argue that this transition corresponds to formation of a bcc ionic crystal. For high densities the ions form an fcc crystal, for which we find a fluctuation-induced first-order charge-ordered-charge-disordered transition, in agreement with recent simulation studies. Our results also shed light on the simulation results obtained for an off-lattice ionic system, for which a schematic phase diagram is constructed.

摘要

为了给在σ/a = 1、σ/a = 2和σ/a≥3(a为晶格常数,σ为离子直径)的模拟中获得的相图的定性差异提供理论基础,在一种场论方法内研究了离子系统的受限原始模型。在具有最近邻(NN)排斥力(0≤J≤∞)并补充库仑力的模型中,研究了从σ/a = 1的情况到σ/a = √2(排除最近邻(NN)占据)的情况的相图演变。在平均场(MF)近似中找到了电荷无序相对于短波长电荷涨落的稳定边界和三临界点。接下来,研究了涨落的影响,我们发现当J超过特定值J0时,应该预期会出现涨落诱导的一级相变,而不是在MF中发现的连续相变。在J = J0时,连续相变线分裂成两条包围两相区域的线,当J≥J0增加时,其厚度从零增加。我们认为这种转变对应于体心立方离子晶体的形成。对于高密度,离子形成面心立方晶体,对此我们发现了涨落诱导的一级电荷有序 - 电荷无序转变,这与最近的模拟研究一致。我们的结果也为非晶格离子系统的模拟结果提供了启示,为此构建了一个示意性相图。

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