Center for Nonlinear Phenomena and Complex Systems, Université Libre de Bruxelles, Blvd. du Triomphe, Code Postal 231,1050 Brussels, Belgium.
J Chem Phys. 2012 Apr 7;136(13):134502. doi: 10.1063/1.3698603.
A recent description of diffusion-limited nucleation based on fluctuating hydrodynamics that extends classical nucleation theory predicts a very non-classical two-step scenario whereby nucleation is most likely to occur in spatially extended, low-amplitude density fluctuations. In this paper, it is shown how the formalism can be used to determine the maximum probability of observing any proposed nucleation pathway, thus allowing one to address the question as to their relative likelihood, including of the newly proposed pathway compared to classical scenarios. Calculations are presented for the nucleation of high-concentration droplets in a low-concentration solution of globular proteins and it is found that the relative probabilities (new theory compared to classical result) for reaching a critical nucleus containing N(c) molecules scales as e(-N(c)/3) thus indicating that for all but the smallest nuclei, the classical scenario is extremely unlikely.
最近基于涨落流体力学的扩散限制成核的描述扩展了经典成核理论，预测了一个非常非经典的两步情景，即成核最有可能发生在空间扩展、低振幅密度涨落中。在本文中，展示了如何使用形式理论来确定观察任何提议的成核途径的最大概率，从而可以解决它们的相对可能性问题，包括与经典情景相比新提出的途径。计算了在低浓度球状蛋白质溶液中高浓度液滴的成核，发现达到包含 N(c)分子的临界核的相对概率（新理论与经典结果相比）按 e(-N(c)/3) 缩放，因此表明对于除最小核之外的所有核，经典情景极不可能。
