Obtaining the solid-liquid interfacial free energy via multi-scheme thermodynamic integration: Ag-ethylene glycol interfaces.
Obtaining the solid-liquid interfacial free energy via multi-scheme thermodynamic integration: Ag-ethylene glycol interfaces.
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通过多方案热力学积分获得固液界面自由能：银-乙二醇界面。
DOI：
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发表时间：
2016
影响因子：
4.4
通讯作者：
K. Fichthorn
中科院分区：
文献类型：
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作者：
Xin Qi;Ya Zhou;K. Fichthorn
固液界面自由能γsl是润湿、成核和晶体生长过程中的一个重要量。尽管已经开发了各种方法来用原子尺度模拟计算γsl，但是对于分子流体和固体之间的多组分界面，这样的计算仍然具有挑战性。我们提出了一种多方案的热力学积分方法，该方法的灵感来自于“劈壁”方法，旨在使用开源模拟软件包获得此类系统的γsl。该方法在两个方面对前人的方法进行了改进。首先，我们将单独的计划，以解决困难时，操纵周期性的边界条件的超级细胞使用开源模拟包。其次，我们引入了一个数值近似，以获得复杂的力场时，解析微分是不容易获得的热力学被积。为了证明这种方法，我们获得了Ag（100）和Ag（111）与乙二醇（EG）之间界面的γsl。这些界面自由能反映了每个面的界面势能。我们还估计熵的接口形成，这些是一致的理论预测的迹象和趋势。对于Ag-EG体系，我们发现对γsl的最大贡献是产生裸露金属表面的自由能。对γsl的第二大贡献来自液-固相互作用。这种用户友好的方法将加速广泛的研究课题的调查，如溶液相形状控制的手性合成中结构导向剂的热力学效应。
The solid-liquid interfacial free energy γsl is an important quantity in wetting, nucleation, and crystal growth. Although various methods have been developed to calculate γsl with atomic-scale simulations, such calculations still remain challenging for multi-component interfaces between molecular fluids and solids. We present a multi-scheme thermodynamic integration method that is inspired by the "cleaving-wall" method and aimed at obtaining γsl for such systems using open-source simulation packages. This method advances two aspects of its predecessor methods. First, we incorporate separate schemes to resolve difficulties when manipulating periodic boundary conditions of the supercell using open-source simulation packages. Second, we introduce a numerical approximation to obtain thermodynamic integrands for complex force fields when an analytical differentiation is not readily available. To demonstrate this method, we obtain γsl for interfaces between Ag(100) and Ag(111) and ethylene glycol (EG). These interfacial free energies mirror interfacial potential energies for each facet. We also estimate entropies of interface formation and these are consistent with theoretical predictions in signs and trends. For the Ag-EG systems, we find that the largest contribution to γsl is the free energy to create the bare metal surfaces. The second-largest contribution to γsl is from the liquid-solid interaction. This user-friendly method will accelerate investigation in a broad range of research topics, such as the thermodynamic effect of structure-directing agents in solution-phase shape-controlled nanocrystal syntheses.
影响因子：
15
作者：
Xia, Xiaohu;Zeng, Jie;Oetjen, L. Kyle;Li, Qingge;Xia, Younan
通讯作者：
Xia, Younan
影响因子：
4.6
作者：
F. Leroy;Daniel J. V. A. dos Santos;F. Müller-Plathe
通讯作者：
F. Leroy;Daniel J. V. A. dos Santos;F. Müller-Plathe
影响因子：
4.4
作者：
Leroy, Frederic;Mueller-Plathe, Florian
通讯作者：
Mueller-Plathe, Florian