Intermolecular potential energy surface and thermophysical properties of propane.
Intermolecular potential energy surface and thermophysical properties of propane.
复制标题
DOI：
10.1063/1.4978412
复制
发表时间：
2017-03
期刊：
影响因子：
--
通讯作者：
R. Hellmann
中科院分区：
文献类型：
--
作者：
R. Hellmann
从超分子从头计算到耦合团簇的单、双和微扰三重激发理论水平，确定了两个刚性丙烷分子相互作用的六维势能面（PES）.一个分析的网站网站与14个网站每个分子的势函数拟合计算的相互作用能。为了验证解析PES的正确性，计算了丙烷的第二维里系数、稀气体剪切粘度和导热系数。对势函数的色散部分进行了轻微调整，使得在室温下第二维里系数与最精确的实验数据定量一致。调整后的PES产量值的三个属性，是在所有温度下的最佳实验数据非常好的协议。
A six-dimensional potential energy surface (PES) for the interaction of two rigid propane molecules was determined from supermolecular ab initio calculations up to the coupled cluster with single, double, and perturbative triple excitations level of theory for 9452 configurations. An analytical site-site potential function with 14 sites per molecule was fitted to the calculated interaction energies. To validate the analytical PES, the second virial coefficient and the dilute gas shear viscosity and thermal conductivity of propane were computed. The dispersion part of the potential function was slightly adjusted such that quantitative agreement with the most accurate experimental data for the second virial coefficient at room temperature was achieved. The adjusted PES yields values for the three properties that are in very good agreement with the best experimental data at all temperatures.