Luber Sandra
Institut für Chemie, Universität Zürich, Winterthurerstrasse 190, 8057 Zürich, Switzerland.
J Chem Phys. 2014 Dec 21;141(23):234110. doi: 10.1063/1.4903828.
We describe a novel approach for the calculation of local electric dipole moments for periodic systems. Since the position operator is ill-defined in periodic systems, maximally localized Wannier functions based on the Berry-phase approach are usually employed for the evaluation of local contributions to the total electric dipole moment of the system. We propose an alternative approach: within a subsystem-density functional theory based embedding scheme, subset electric dipole moments are derived without any additional localization procedure, both for hybrid and non-hybrid exchange-correlation functionals. This opens the way to a computationally efficient evaluation of local electric dipole moments in (molecular) periodic systems as well as their rigorous splitting into atomic electric dipole moments. As examples, Infrared spectra of liquid ethylene carbonate and dimethyl carbonate are presented, which are commonly employed as solvents in Lithium ion batteries.
我们描述了一种计算周期性系统局部电偶极矩的新方法。由于位置算符在周期性系统中定义不明确，基于贝里相位方法的最大局域化万尼尔函数通常用于评估系统总电偶极矩的局部贡献。我们提出了一种替代方法：在基于子系统密度泛函理论的嵌入方案中，无需任何额外的局域化过程即可导出子集电偶极矩，适用于混合和非混合交换相关泛函。这为在（分子）周期性系统中高效计算局部电偶极矩以及将其严格分解为原子电偶极矩开辟了道路。作为示例，给出了碳酸亚乙酯和碳酸二甲酯液体的红外光谱，它们通常用作锂离子电池的溶剂。
