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受限在两个带电板之间的二聚体的性质。

The properties of dimers confined between two charged plates.

机构信息

School of Chemical Engineering and Analytical Science, The University of Manchester, P.O. Box 88, Sackville Street, M60 1QD Manchester, United Kingdom.

出版信息

J Chem Phys. 2010 Mar 21;132(11):114102. doi: 10.1063/1.3354121.

Abstract

We consider two like-charged planar surfaces immersed in solution of oppositely charged dimer counterions with a bond length l. To analyze this system, we extend and employ a self-consistent field theory that has been shown to be accurate from the weak to the intermediate through to the strong coupling regimes. In the limit of very short dimers, the results converge to the results for pointlike divalent ions. Near the surfaces, the dimers lie parallel to the charged plates. In the intermediate coupling regime, the dimers are aligned perpendicularly to the surface when they are a distance l from a surface. In the weak coupling regime, the interactions are only repulsive. At slightly higher couplings, there is a minimum in the variation of the free energy with distance at approximately the bond length of the dimers, which arises from bridging conformations of the dimers. In the intermediate coupling regime, an additional minimum in the free energy is observed at much smaller distances, which is due to the correlations between the dimers. For large dimer bond lengths, this minimum is metastable with respect to the previous minimum. However, as the bond length decreases, this minimum becomes the stable, while the minimum associated with the dimer bond length becomes metastable and eventually disappears. For shorter dimer bond length the attractive interaction is the result of correlations between counterions and charges on the surfaces. We find that dimers can mediate attractive interaction between like-charged surfaces in the intermediate coupling regime. The analysis of orientations confirms the bridging mechanism for sufficiently long dimers, whereas at high electrostatic couplings charge correlations contribute to the attraction.

摘要

我们考虑两个带相同电荷的平面浸入到带有键长 l 的相反电荷二聚体抗衡离子的溶液中。为了分析这个系统,我们扩展并运用了自洽场理论,该理论已被证明在弱耦合到中等耦合再到强耦合的范围内是准确的。在非常短的二聚体极限下,结果收敛到点状二价离子的结果。在靠近表面的地方,二聚体平行于带电板。在中等耦合范围内,当二聚体距离表面 l 时,它们垂直于表面排列。在弱耦合范围内,相互作用仅为排斥。在稍高的耦合下,在大约二聚体键长处,自由能随距离的变化会出现最小值,这是由于二聚体的桥接构象所致。在中等耦合范围内,在更小的距离处观察到自由能的额外最小值,这是由于二聚体之间的相关性所致。对于较大的二聚体键长,这个最小值相对于先前的最小值是亚稳定的。然而,随着键长的减小,这个最小值成为稳定的,而与二聚体键长相关的最小值成为亚稳定的,并最终消失。对于更短的二聚体键长,吸引力是抗衡离子和表面电荷之间相关性的结果。我们发现,在中等耦合范围内,二聚体能介导带相同电荷的表面之间的吸引力。取向分析证实了足够长的二聚体的桥接机制,而在高静电耦合下,电荷相关性会导致吸引力。

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