Vehkamäki Hanna, Määttänen Anni, Lauri Antti, Kulmala Markku, Winkler Paul, Vrtala Aron, Wagner Paul E
Department of Physical Sciences, P.O. Box 64, University of Helsinki, 00014 Helsinki, Finland.
J Chem Phys. 2007 May 7;126(17):174707. doi: 10.1063/1.2723073.
In this paper we present a new form of the nucleation theorems applicable to heterogeneous nucleation. These heterogeneous nucleation theorems allow, for the first time, direct determination of properties of nanoclusters formed on pre-existing particles from measured heterogeneous nucleation probabilities. The theorems can be used to analyze the size (first theorem) and the energetics (second theorem) of heterogeneous clusters independent of any specific nucleation model. We apply the first theorem to the study of small water and n-propanol clusters formed at the surface of 8 nm silver particles. According to the experiments the size of the two-component critical clusters is found to be below 90 molecules, and only less than 20 molecules for pure water, less than 300 molecules for pure n-propanol. These values are drastically smaller than the ones predicted by the classical nucleation theory, which clearly indicates that the nucleating clusters are too small to be quantitatively described using a macroscopic theory.
在本文中,我们提出了一种适用于异质成核的新形式的成核定理。这些异质成核定理首次允许根据测量的异质成核概率直接确定在预先存在的颗粒上形成的纳米团簇的性质。这些定理可用于分析异质团簇的尺寸(第一定理)和能量学(第二定理),而无需依赖任何特定的成核模型。我们将第一定理应用于研究在8纳米银颗粒表面形成的小水团簇和正丙醇团簇。根据实验,发现两组分临界团簇的尺寸小于90个分子,对于纯水仅小于20个分子,对于纯正丙醇小于300个分子。这些值比经典成核理论预测的值小得多,这清楚地表明成核团簇太小,无法用宏观理论进行定量描述。