Borodin Oleg
Wasatch Molecular Inc., 2141 St. Marys Drive, Suite 102, Salt Lake City, Utah 84108, USA.
J Phys Chem B. 2009 Sep 10;113(36):12353-7. doi: 10.1021/jp9070357.
A number of correlations between heat of vaporization (H(vap)), cation-anion binding energy (E(+/-)), molar volume (V(m)), self-diffusion coefficient (D), and ionic conductivity for 29 ionic liquids have been investigated using molecular dynamics (MD) simulations that employed accurate and validated many-body polarizable force fields. A significant correlation between D and H(vap) has been found, while the best correlation was found for -log(DV(m)) vs H(vap) + 0.28E(+/-). A combination of enthalpy of vaporization and a fraction of the cation-anion binding energy was suggested as a measure of the effective cohesive energy for ionic liquids. A deviation of some ILs from the reported master curve is explained based upon ion packing and proposed diffusion pathways. No general correlations were found between the ion diffusion coefficient and molecular volume or the diffusion coefficient and cation/anion binding energy.
使用采用精确且经过验证的多体极化力场的分子动力学（MD）模拟，研究了29种离子液体的汽化热（H(vap)）、阳离子 - 阴离子结合能（E(+/-)）、摩尔体积（V(m)）、自扩散系数（D）和离子电导率之间的若干相关性。发现D与H(vap)之间存在显著相关性，而 -log(DV(m)) 与H(vap) + 0.28E(+/-)之间的相关性最佳。有人提出将汽化焓和阳离子 - 阴离子结合能的一部分相结合，作为离子液体有效内聚能的一种度量。基于离子堆积和提出的扩散途径，解释了一些离子液体与报道的主曲线的偏差。未发现离子扩散系数与分子体积之间或扩散系数与阳离子/阴离子结合能之间存在普遍相关性。
