Center for Nonlinear Phenomena and Complex Systems, Code Postal 231, Université Libre de Bruxelles, Blvd. du Triomphe, 1050 Brussels, Belgium.
J Chem Phys. 2012 Jan 21;136(3):034509. doi: 10.1063/1.3677191.
A general theory of nucleation for colloids and macromolecules in solution is formulated within the context of fluctuating hydrodynamics. A formalism for the determination of nucleation pathways is developed and stochastic differential equations for the evolution of order parameters are given. The conditions under which the elements of classical nucleation theory are recovered are determined. The theory provides a justification and extension of more heuristic equilibrium approaches based solely on the free energy. It is illustrated by application to the low-concentration/high-concentration transition in globular proteins, where a novel two-step mechanism is identified, where the first step involves the formation of long-wavelength density fluctuations, and the second step is the actual nucleation event occurring within the fluctuation.
本文在涨落流体力学的框架内，为胶体和溶液中的高分子建立了成核的一般理论。文中提出了确定成核途径的形式体系，并给出了序参量演化的随机微分方程。确定了经典成核理论元素得以恢复的条件。该理论为仅基于自由能的更启发式的平衡方法提供了合理性和扩展。通过应用于球蛋白的低浓度/高浓度转变来说明，确定了一个新的两步机制，其中第一步涉及长波长密度涨落的形成，第二步是在涨落内发生的实际成核事件。
