AI 中文总结
研究气相成核问题，基于长程分子间力构建三分子反应网络理论，涵盖单组分与二元混合物情况，纳入团簇蒸发扩展框架，经水、甲苯和丁烷成核测试，确定长程力为驱动力，确立三分子化学为团簇形成预测途径。
AI 中文摘要
新相的产生通常从热力学角度描述，但在气相中它始于化学过程。本文表明气相成核可描述为由长程分子间力主导的三分子反应网络。在单组分混合物中，二聚体形成是直接的三分子过程；在二元混合物中，伴随机制可增强成核，第二种组分充当团簇形成的催化剂。通过纳入团簇蒸发，该框架可扩展到碰撞极限之外，为更大临界团簇相关的区域提供成核的分子途径。我们用该理论测试水、甲苯和丁烷的一元及二元成核，在探索的温度和密度范围内绝对速率在一个数量级内达成一致。这些结果确定长程分子间力为气相成核的分子驱动力，并确立基本三分子化学为团簇形成的预测途径。
英文摘要
The birth of a new phase is usually described thermodynamically, but in the gas phase it begins as chemistry. Here, we show that gas-phase nucleation can be described as a termolecular reaction network controlled primarily by long-range intermolecular forces. In single-component mixtures, dimer formation emerges as a direct termolecular process, whereas in binary mixtures a chaperon mechanism can enhance nucleation, with the second component acting as a catalyst for cluster formation. By incorporating cluster evaporation, the same framework can be extended beyond the collision limit, providing a molecular route to nucleation in regimes where larger critical clusters become relevant. We test the theory against unary and binary nucleation of water, toluene, and butane, obtaining agreement in absolute rates within one order of magnitude across the explored temperature and density ranges. These results identify long-range intermolecular forces as molecular drivers of gas-phase nucleation and establish elementary termolecular chemistry as a predictive route to cluster formation.
Comments25 pages, 10 figures
