Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
J Chem Phys. 2011 Jun 21;134(23):234705. doi: 10.1063/1.3598484.
Though the local dielectric constant at interfaces is an important phenomenological parameter in the analysis of surface spectroscopy, its microscopic definition has been uncertain. Here, we present a full molecular theory on the local field at interfaces with the help of molecular dynamics simulation, and thereby provide microscopic basis for the local dielectric constant so as to be consistent to the phenomenological three-layer model of interface systems. To demonstrate its performance, we applied the theory to the water/vapor interface, and obtained the local field properties near the interface where the simple dielectric model breaks down. Some computational issues pertinent to Ewald calculations of the dielectric properties are also discussed.
虽然界面处的局部介电常数是分析表面光谱学的一个重要现象参数，但它的微观定义一直不确定。在这里，我们借助分子动力学模拟，对界面处的局域场提出了一个完整的分子理论，从而为局部介电常数提供了微观基础，使其与界面系统的三层模型相一致。为了证明其性能，我们将该理论应用于水/汽界面，并获得了简单介电模型失效的界面附近的局域场性质。还讨论了与介电性质的 Ewald 计算相关的一些计算问题。
