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arXiv 2009.07017cond-mat.stat-mechmath-phmath.MP
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Smoluchowski的困惑:聚合的统计力学

The Smoluchowski Ensemble: Statistical Mechanics of Aggregation

Themis Matsoukas

摘要:

我们提出了一个严格的热力学处理不可逆的二元聚集。我们构建的Smoluchowski合奏作为一组离散的有限分布产生的所有单体相同的初始状态后,固定数量的合并事件,并定义一个概率测量这个合奏,这样的平均分布在平均场近似由Smoluchowski方程。在标度极限下,这个系综产生了一组完全类似于熟悉的统计热力学的关系。热力学处理的中心元素是选择泛函,一个可行分布的泛函,它将分布的概率与聚集模型的具体细节联系起来。我们得到一般内核和封闭形式的结果的特殊情况下的常数,总和和产品的内核的缩放表达式。我们研究了最概然分布的稳定性,为溶胶-凝胶转变提供了判据,并通过简单的热力学参数得到了凝胶后区域的分布。

英文摘要:

We present a rigorous thermodynamic treatment of irreversible binary aggregation. We construct the Smoluchowski ensemble as the set of discrete finite distributions generated from the same initial state of all monomers upon fixed number merging events and define a probability measure on this ensemble such that the mean distribution in the mean-field approximation is governed by the Smoluchowski equation. In the scaling limit this ensemble gives rise to a set of relationships completely analogous to those of familiar statistical thermodynamics. The central element of the thermodynamic treatment is the selection functional, a functional of feasible distributions that connects the probability of distribution to the specific details of the aggregation model. We obtain scaling expressions for general kernels and closed-form results for the special case of the constant, sum and product kernel. We study the stability of the most probable distribution, provide criteria for the sol-gel transition and obtain the distribution in the post-gel region by simple thermodynamic arguments.

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