Jin Jaehyeok, Pak Alexander J, Han Yining, Voth Gregory A
Department of Chemistry, Chicago Center for Theoretical Chemistry, Institute for Biophysical Dynamics, and James Franck Institute, The University of Chicago, Chicago, Illinois 60637, USA.
J Chem Phys. 2021 Jan 28;154(4):044105. doi: 10.1063/5.0026652.
A number of studies have constructed coarse-grained (CG) models of water to understand its anomalous properties. Most of these properties emerge at low temperatures, and an accurate CG model needs to be applicable to these low-temperature ranges. However, direct use of CG models parameterized from other temperatures, e.g., room temperature, encounters a problem known as transferability, as the CG potential essentially follows the form of the many-body CG free energy function. Therefore, temperature-dependent changes to CG interactions must be accounted for. The collective behavior of water at low temperature is generally a many-body process, which often motivates the use of expensive many-body terms in the CG interactions. To surmount the aforementioned problems, we apply the Bottom-Up Many-Body Projected Water (BUMPer) CG model constructed from Paper I to study the low-temperature behavior of water. We report for the first time that the embedded three-body interaction enables BUMPer, despite its pairwise form, to capture the growth of ice at the ice/water interface with corroborating many-body correlations during the crystal growth. Furthermore, we propose temperature transferable BUMPer models that are indirectly constructed from the free energy decomposition scheme. Changes in CG interactions and corresponding structures are faithfully recapitulated by this framework. We further extend BUMPer to examine its ability to predict the structure, density, and diffusion anomalies by employing an alternative analysis based on structural correlations and pairwise potential forms to predict such anomalies. The presented analysis highlights the existence of these anomalies in the low-temperature regime and overcomes potential transferability problems.
许多研究构建了水的粗粒度(CG)模型,以了解其反常性质。这些性质大多在低温下出现,因此准确的CG模型需要适用于这些低温范围。然而,直接使用从其他温度(如室温)参数化的CG模型会遇到所谓的可转移性问题,因为CG势本质上遵循多体CG自由能函数的形式。因此,必须考虑CG相互作用随温度的变化。低温下水的集体行为通常是一个多体过程,这常常促使在CG相互作用中使用昂贵的多体项。为了克服上述问题,我们应用第一篇论文中构建的自底向上多体投影水(BUMPer)CG模型来研究水的低温行为。我们首次报告,尽管BUMPer具有成对形式,但其中嵌入的三体相互作用使其能够在冰/水界面捕捉冰的生长,并在晶体生长过程中证实多体相关性。此外,我们提出了通过自由能分解方案间接构建的温度可转移BUMPer模型。该框架忠实地再现了CG相互作用和相应结构的变化。我们进一步扩展了BUMPer,通过采用基于结构相关性和成对势形式的替代分析来预测结构、密度和扩散异常,以检验其预测这些异常的能力。所呈现的分析突出了这些异常在低温区域的存在,并克服了潜在的可转移性问题。