气液成核的速率理论:追求难以捉摸的定量准确性

Subhajit Acharya, Biman Bagchi
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引用次数: 0

摘要

尽管在大过饱和度条件下进行的无偏模拟研究已经取得了可靠的结果,但对气液成核速率进行第一性原理理论计算的任务在很大程度上仍未完成。尽管贝克尔-多林-泽尔多维奇(Becker-Doring-Zeldovich)在大约一个世纪前提出的经典成核理论为一阶相变中的成核提供了一个优雅的、被广泛使用的图景,但该理论在准确预测速率方面存在困难,尤其是在气-液成核的情况下。在这里,我们使用多阶参数描述来构建计算成核率所需的成核自由能面。多维非马尔可夫(MDNM)速率理论表述通过使用格罗特-海因斯 MDNM 处理方法对兰格著名的成核理论进行了概括,从而获得了越障速率。我们发现该理论与通过直接无偏分子动力学模拟获得的速率非常吻合--后者在高过饱和度 S 条件下是可行的。这源于阻挡层表面的多次重越。我们发现马尔可夫理论(如朗格公式)无法定量捕捉这一速率。此外,多维过渡态理论表达也表现不佳,揭示了摩擦系数的潜在作用。
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Rate theory of gas–liquid nucleation: Quest for the elusive quantitative accuracy
The task of a first principles theoretical calculation of the rate of gas–liquid nucleation has remained largely incomplete despite the existence of reliable results from unbiased simulation studies at large supersaturation. Although the classical nucleation theory formulated by Becker–Doring–Zeldovich about a century ago provides an elegant, widely used picture of nucleation in a first-order phase transition, the theory finds difficulties in predicting the rate accurately, especially in the case of gas-to-liquid nucleation. Here, we use a multiple-order parameter description to construct the nucleation free energy surface needed to calculate the nucleation rate. A multidimensional non-Markovian (MDNM) rate theory formulation that generalizes Langer’s well-known nucleation theory by using the Grote–Hynes MDNM treatment is used to obtain the rate of barrier crossing. We find good agreement of the theory with the rate obtained by direct unbiased molecular dynamics simulations—the latter is feasible at large supersaturation, S. The theory gives an experimentally strong dependence of the rate of nucleation on supersaturation, S. Interestingly, we find a strong influence of the frequency-dependent friction coefficient at the barrier top. This arises from multiple recrossings of the barrier surface. We find that a Markovian theory, such as Langer’s formulation, fails to capture the rate quantitatively. In addition, the multidimensional transition state theory expression performs poorly, revealing the underlying role of the friction coefficient.
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