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arXiv 1209.2648physics.chem-phcond-mat.softcond-mat.stat-mech
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晶体成核的布朗模型

A Brownian Model for Crystal Nucleation

Miguel A. Durán-Olivencia, Fermín Otálora

摘要:

在这项工作中,提出了一个唯象的随机微分方程模型的半径的时间演化的前临界分子团簇在成核(经典的序参量)。这样一个随机微分方程构成的基础上计算的(成核)诱导时间根据Kramers的热激活逃逸过程的理论。考虑成核阶段作为一个泊松稀有事件,解析表达式的诱导时间统计推导出稳定和非稳定条件下,后者假设半绝热极限。这些表达式可用于识别分子团簇形成的潜在机制(从成核统计中区分均匀成核或非均匀成核是可能的)以及预测诱导时间和诱导时间分布。该模型的预测是在良好的协议与实验测得的感应时间在恒定的温度下,从经典方程得到的值不同,但协议是不是那么好的感应时间统计。随机模拟截断的最大等待时间的实验证实,这一事实是由于实验所施加的时间限制。校正这种影响,实验和预测曲线拟合得非常好。因此,所提出的模型似乎是一个通用的工具,以预测团簇尺寸分布,成核速率,(成核)诱导时间和诱导时间的统计范围广泛的条件(例如,时间依赖性的温度,过饱和度,pH值等)。其中经典成核理论的适用性有限。

英文摘要:

In this work a phenomenological stochastic differential equation is proposed to model the time evolution of the radius of a pre-critical molecular cluster during nucleation (the classical order parameter). Such a stochastic differential equation constitutes the basis for the calculation of the (nucleation) induction time under Kramers' theory of thermally activated escape processes. Considering the nucleation stage as a Poisson rare-event, analytical expressions for the induction time statistics are deduced for both steady and unsteady conditions, the latter assuming the semiadiabatic limit. These expressions can be used to identify the underlying mechanism of molecular cluster formation (distinguishing between homogeneous or heterogeneous nucleation from the nucleation statistics is possible) as well as to predict induction times and induction time distributions. The predictions of this model are in good agreement with experimentally measured induction times at constant temperature, unlike the values obtained from the classical equation, but agreement is not so good for induction time statistics. Stochastic simulations truncated to the maximum waiting time of the experiments confirm that this fact is due to the time constraints imposed by experiments. Correcting for this effect, the experimental and predicted curves fit remarkably well. Thus, the proposed model seems to be a versatile tool to predict cluster size distributions, nucleation rates, (nucleation) induction time and induction time statistics for a wide range of conditions (e.g. time-dependent temperature, supersaturation, pH, etc.) where classical nucleation theory is of limited applicability.

机构、总结、中文摘要均由AI分析而来,可能存在错误,请以论文正文为准。

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