Intermolecular Interactions and Local Density Augmentation in Supercritical Solvation: A Survey of Simulation and Experimental Results
Intermolecular Interactions and Local Density Augmentation in Supercritical Solvation: A Survey of Simulation and Experimental Results
复制标题
超临界溶剂化中的分子间相互作用和局部密度增强：模拟和实验结果综述
DOI：
10.1021/jp000888d
复制
发表时间：
2000
影响因子：
2.9
通讯作者：
M. Maroncelli
中科院分区：
文献类型：
--
作者：
W. Song;R. Biswas;M. Maroncelli
从先前的模拟和实验研究（总共52个溶质/溶剂对）中收集和分析数据，试图将超临界流体中局部密度增加的程度与分子间相互作用的强度联系起来。为此，构建了由原子-原子成对相加势组成的分子间势函数，参数取自文献资料或量子化学计算，并根据实验二压维里系数数据进行了测试。对于室温附近超临界系统中溶质-溶剂组合，发现这些势能以合理的精度再现实验二压维里系数数据。在这些电位的基础上，计算了溶质-溶剂和溶剂-溶剂相互作用的各种特性，并与密度增加的模拟和实验测量进行了比较。结果表明，增大的幅度较大。
Data from prior simulation and experimental studies (a total of 52 solute/solvent pairs) are collected and analyzed in an attempt to relate the extent of local density augmentation in supercritical fluids to the strength of intermolecular interactions. For this purpose, intermolecular potential functions consisting of pairwise additive atom−atom potentials, with parameters either taken from literature sources or derived from quantum chemical calculations, are constructed and tested against experimental second-pressure virial coefficient data. For the solute−solvent combinations of interest in supercritical systems near room temperature, such potentials are found to reproduce experimental second-pressure virial coefficient data with reasonable accuracy. On the basis of these potentials, a variety of characteristics of solute−solvent and solvent−solvent interactions are computed and compared to simulated and experimental measures of density augmentation. It is found that the extent of augmentation is strong...