论文标题
结构形成系统的热力学
Thermodynamics of structure-forming systems
论文作者
论文摘要
结构形成的系统本质上是普遍存在的，从原子建立分子到胶体两性胞质颗粒的自组装。对此类系统的基础热力学的理解仍然是一个重要的问题。在这里，我们通过明确捕获聚类状态的术语来得出与玻尔兹曼·吉布斯熵不同的结构形成系统的熵。对于大型系统和低浓度，该方法等同于大型典型的合奏。对于小型系统，我们发现巨大的偏差。我们为结构形成系统提供了详细的波动定理和Crooks的工作波动定理。讨论了与粒子自组装理论的联系。我们将结果应用于几个物理系统。我们介绍了由Kern-Frenkel电位描述的片状颗粒的相图。我们表明，带有分子结构的库里 - 韦斯模型表现出一阶相变。
Structure-forming systems are ubiquitous in nature, ranging from atoms building molecules to self-assembly of colloidal amphibolic particles. The understanding of the underlying thermodynamics of such systems remains an important problem. Here we derive the entropy for structure-forming systems that differs from Boltzmann-Gibbs entropy by a term that explicitly captures clustered states. For large systems and low concentrations, the approach is equivalent to the grand-canonical ensemble; for small systems, we find significant deviations. We derive the detailed fluctuation theorem and Crooks' work fluctuation theorem for structure-forming systems. The connection to the theory of particle self-assembly is discussed. We apply the results to several physical systems. We present the phase diagram for patchy particles described by the Kern-Frenkel potential. We show that the Curie-Weiss model with molecule structures exhibits a first-order phase transition.
