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平均场动力学成核理论

Mean-field kinetic nucleation theory.

作者信息

Kalikmanov V I

机构信息

Twister Supersonic Gas Solutions, Einsteinlaan 10, 2289 CC, Rijswijk, The Netherlands.

出版信息

J Chem Phys. 2006 Mar 28;124(12):124505. doi: 10.1063/1.2178812.

Abstract

A new semiphenomenological model of homogeneous vapor-liquid nucleation is proposed in which the cluster kinetics follows the "kinetic approach to nucleation" and the thermodynamic part is based on the revised Fisher droplet model with the mean-field argument for the cluster configuration integral. The theory is nonperturbative in a cluster size and as such is valid for all clusters down to monomers. It contains two surface tensions: macroscopic (planar) and microscopic. The latter is a temperature dependent quantity related to the vapor compressibility factor at saturation. For Lennard-Jones fluids the microscopic surface tension possesses a universal behavior with the parameters found from the mean-field density functional calculations. The theory is verified against nucleation experiments for argon, nitrogen, water, and mercury, demonstrating very good agreement with experimental data. Classical nucleation theory fails to predict experimental results when a critical cluster becomes small.

摘要

提出了一种新的均相气-液成核半唯象模型,其中团簇动力学遵循“成核动力学方法”,热力学部分基于修正的费舍尔液滴模型,并采用平均场理论处理团簇构型积分。该理论在团簇尺寸方面是非微扰的,因此对直至单体的所有团簇均有效。它包含两种表面张力:宏观(平面)表面张力和微观表面张力。后者是一个与饱和时蒸汽压缩因子相关的温度依赖量。对于 Lennard-Jones 流体,微观表面张力具有普适行为,其参数可通过平均场密度泛函计算得到。该理论通过氩气、氮气、水和汞的成核实验得到验证,与实验数据显示出非常好的一致性。当临界团簇变小时,经典成核理论无法预测实验结果。

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