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Buckling a Semiflexible Polymer Chain under Compression

机译:在压缩下屈曲半柔性聚合物链

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Instability and structural transitions arise in many important problems involving dynamics at molecular length scales. Buckling of an elastic rod under a compressive load offers a useful general picture of such a transition. However, the existing theoretical description of buckling is applicable in the load response of macroscopic structures, only when fluctuations can be neglected, whereas membranes, polymer brushes, filaments, and macromolecular chains undergo considerable Brownian fluctuations. We analyze here the buckling of a fluctuating semiflexible polymer experiencing a compressive load. Previous works rely on approximations to the polymer statistics, resulting in a range of predictions for the buckling transition that disagree on whether fluctuations elevate or depress the critical buckling force. In contrast, our theory exploits exact results for the statistical behavior of the worm-like chain model yielding unambiguous predictions about the buckling conditions and nature of the buckling transition. We find that a fluctuating polymer under compressive load requires a larger force to buckle than an elastic rod in the absence of fluctuations. The nature of the buckling transition exhibits a marked change from being distinctly second order in the absence of fluctuations to being a more gradual, compliant transition in the presence of fluctuations. We analyze the thermodynamic contributions throughout the buckling transition to demonstrate that the chain entropy favors the extended state over the buckled state, providing a thermodynamic justification of the elevated buckling force.
机译:在涉及分子尺度动力学的许多重要问题中,都出现了不稳定性和结构转变。弹性杆在压缩载荷下的屈曲提供了这种过渡的有用的一般情况。但是,现有的屈曲理论描述仅在可以忽略波动的情况下才适用于宏观结构的载荷响应,而膜,聚合物刷,细丝和大分子链则经历相当大的布朗波动。我们在这里分析经历压缩载荷的波动半柔性聚合物的屈曲。先前的工作依赖于聚合物统计数据的近似值,从而导致对屈曲转变的一系列预测,这些预测与波动是升高还是降低临界屈曲力不一致。相比之下,我们的理论利用蠕虫状链模型的统计行为的精确结果,对屈曲条件和屈曲过渡的性质做出了明确的预测。我们发现,在没有波动的情况下,在压缩载荷下波动的聚合物比弹性杆需要更大的屈曲力。屈曲过渡的性质呈现出显着的变化,从没有波动的明显二阶变化到存在波动的更为渐进的顺应性转换。我们分析了整个屈曲过渡过程中的热力学贡献,以证明链熵比屈曲状态更有利于延伸状态,从而提供了提高的屈曲力的热力学依据。

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