Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
J Chem Phys. 2018 Sep 28;149(12):124108. doi: 10.1063/1.5046511.
Using a variational field-theoretic approach, we derive a theory for polar fluids. The theory naturally accounts for the reaction field without resorting to the cavity construct and leads to a simple formula for the dielectric constant in terms of the molecular dipole moment and density. We apply our formula to calculate the dielectric constants of nonpolarizable liquid models for more than a hundred small molecules without using any adjustable parameters. Our formula predicts dielectric constants of these nonpolarizable liquid models more accurately than the Onsager theory and previous field-theoretic dielectric theories, as demonstrated by the closer agreement to the simulation results. The general theory also yields the free energy, which can describe the response of polar fluids under applied electric fields.
我们使用变分场论方法推导出了一个关于极性流体的理论。该理论自然地考虑了反应场，而无需采用空洞构造，并得出了一个简单的介电常数公式，该公式与分子偶极矩和密度有关。我们应用该公式计算了一百多种非极化液体模型的介电常数，而无需使用任何可调参数。与 Onsager 理论和以前的场论介电理论相比，我们的公式更准确地预测了这些非极化液体模型的介电常数，这一点从与模拟结果的更吻合得到了证明。该普遍理论还给出了自由能，可以描述极性流体在电场作用下的响应。
