Insight into the Density-Dependence of Pair Potentials for Predictive Coarse-Grained Models
Insight into the Density-Dependence of Pair Potentials for Predictive Coarse-Grained Models
复制标题
洞察预测粗粒度模型对势的密度依赖性
DOI：
10.1021/acs.jpcb.3c06890
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发表时间：
2024
期刊：
影响因子：
--
通讯作者：
Noid, W. G.
中科院分区：
文献类型：
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作者：
Lesniewski, Maria C.;Noid, W. G.
我们研究了1，4-二氧六环和四氢呋喃两种工业溶剂的单中心粗粒（CG）模型的有效对势随温度和密度的变化。我们观察到，计算的对势是更敏感的密度比温度。广义Yvon Born-Green框架表明，这种惊人的密度依赖性反映了多体相关性的相应变化，这些相关性决定了环境介导的对平均力的间接贡献。此外，我们证明，也许令人惊讶的是，这种密度依赖性是不重要的精确建模的分子间结构。相应地，我们采用了一个与密度无关的相互作用势，并将计算得到的对势的密度依赖性转化为与组态无关的体积势。此外，我们开发了一个单一的全球潜力，准确地模拟分子间的结构和压力-体积状态方程在很宽的范围内的液态点。因此，这项工作提供了基本的洞察有效对电位的密度依赖性，也提供了一个重要的一步，发展预测CG模型，有效地模拟工业溶剂。
We investigate the temperature- and density-dependence of effective pair potentials for 1-site coarse-grained (CG) models of two industrial solvents, 1,4-dioxane and tetrahydrofuran. We observe that the calculated pair potentials are much more sensitive to density than to temperature. The generalized-Yvon-Born–Green framework reveals that this striking density-dependence reflects corresponding variations in the many-body correlations that determine the environment-mediated indirect contribution to the pair mean force. Moreover, we demonstrate, perhaps surprisingly, that this density-dependence is not important for accurately modeling the intermolecular structure. Accordingly, we adopt a density-independent interaction potential and transfer the density-dependence of the calculated pair potentials into a configuration-independent volume potential. Furthermore, we develop a single global potential that accurately models the intermolecular structure and pressure–volume equation of state across a very wide range of liquid state points. Consequently, this work provides fundamental insight into the density-dependence of effective pair potentials and also provides a significant step toward developing predictive CG models for efficiently modeling industrial solvents.