Pestana Luis Ruiz, Minnetian Natalie, Lammers Laura Nielsen, Head-Gordon Teresa
Chemical Sciences Division , Lawrence Berkeley National Laboratory , University of California , Berkeley , USA . Email:
Department of Chemistry , University of California , Berkeley , USA.
Chem Sci. 2018 Jan 2;9(6):1640-1646. doi: 10.1039/c7sc03524a. eCollection 2018 Feb 14.
When driven out of equilibrium, many diverse systems can form complex spatial and dynamical patterns, even in the absence of attractive interactions. Using kinetic Monte Carlo simulations, we investigate the phase behavior of a binary system of particles of dissimilar size confined between semiflexible planar surfaces, in which the nanoconfinement introduces a non-local coupling between particles, which we model as an activation energy barrier to diffusion that decreases with the local fraction of the larger particle. The system autonomously reaches a cyclical non-equilibrium state characterized by the formation and dissolution of metastable micelle-like clusters with the small particles in the core and the large ones in the surrounding corona. The power spectrum of the fluctuations in the aggregation number exhibits 1/ noise reminiscent of self-organized critical systems. We suggest that the dynamical metastability of the micellar structures arises from an inversion of the energy landscape, in which the relaxation dynamics of one of the species induces a metastable phase for the other species.
当偏离平衡态时,许多不同的系统即使在没有吸引相互作用的情况下也能形成复杂的空间和动力学模式。我们使用动力学蒙特卡罗模拟方法,研究了被限制在半柔性平面表面之间的不同尺寸二元粒子系统的相行为,其中纳米限域在粒子之间引入了非局部耦合,我们将其建模为扩散的活化能垒,该能垒随较大粒子的局部比例降低。该系统自主地达到一个周期性非平衡态,其特征是形成和溶解亚稳的胶束状聚集体,核心为小粒子,周围晕层为大粒子。聚集体数量波动的功率谱呈现出类似于自组织临界系统的1/f噪声。我们认为,胶束结构的动力学亚稳性源于能量景观的反转,其中一种粒子的弛豫动力学为另一种粒子诱导出一个亚稳相。