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Hidden Criticality of Counterion Condensation Near a Charged Cylinder

机译:荷电缸附近平衡离子冷凝的隐藏临界点

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摘要

Counterion condensation onto a charged cylinder, known as the Manning transition, has received a great deal of attention since it is essential to understand the properties of polyelectrolytes in ionic solutions. However, the current understanding is still far from complete and poses a puzzling question: While the strong-coupling theory valid at large ionic correlations suggests a discontinuous nature of the counterion condensation, the mean-field theory always predicts a continuous transition at the same critical point. This naturally leads to a question how one can reconcile the mean-field theory with the strong-coupling prediction. Here, we study the counterion condensation transition on a charged cylinder via Monte Carlo simulations. Varying the cylinder radius systematically in relation to the system size, we find that in addition to the Manning transition, there exists a novel transition where all counterions are bound to the cylinder and the heat capacity shows a drop at a finite Manning parameter. A finite-size scaling analysis is carried out to confirm the criticality of the complete condensation transition, yielding the same critical exponents with the Manning transition. We show that the existence of the complete condensation is essential to explain how the condensation nature alters from continuous to discontinuous transition.
机译:抗衡离子在带电荷圆柱体上的缩合反应(称为曼宁跃迁)受到了广泛关注,因为必须了解离子溶液中聚电解质的性质。但是,目前的理解还远远不够完整,并提出了一个令人费解的问题:尽管在大的离子相关性下有效的强耦合理论表明抗衡离子缩合的不连续性,但平均场理论始终预测在相同临界值下的连续过渡。点。这自然引发了一个问题,即如何将平均场理论与强耦合预测相协调。在这里,我们通过蒙特卡洛模拟研究带电圆柱体上的抗衡离子缩合转变。我们发现,相对于系统尺寸,系统地改变圆柱体半径,我们发现,除了曼宁跃迁之外,还有一个新颖的跃迁,其中所有抗衡离子都结合到圆柱体上,并且热容量在有限的曼宁参数下显示出下降。进行了有限尺寸的比例分析,以确认完全凝结转变的临界度,得出与曼宁转变相同的临界指数。我们表明,完全凝结的存在对于解释凝结性质如何从连续转变为不连续转变至关重要。

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