Counting Electrons in Electrides
Counting Electrons in Electrides
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计算电子化合物中的电子
DOI：
10.1021/jacs.3c10876
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发表时间：
2023
影响因子：
15
通讯作者：
Warren, Scott C.
中科院分区：
文献类型：
--
作者：
Weaver, Samuel M.;Sundberg, Jack D.;Slamowitz, Connor C.;Radomsky, Rebecca C.;Lanetti, Matthew G.;McRae, Lauren M.;Warren, Scott C.
电荷积分方法的选择和设计仍然是材料化学中的一个突出挑战。在像电子这样的复杂材料中，电子波函数的小电荷和复杂形状放大了这一挑战。由于这些原因，流行的积分方法，如贝德方法，通常不能给电子中的裸电子分配任何电荷。为了解决这一挑战，我们开发了一种基于电子局域函数(ELF)来划分电荷的算法，ELF是一种用于可视化分子和固体中重要化学特征的流行方案。该算法使用Bader分割的ELF来寻找电子，使用Voronoi分割的ELF来识别原子。我们应用这种方法“BadELF”来量化离子化合物和电子中的原子半径和氧化态。对于离子化合物，我们发现BadELF方法得到的半径与Shannon晶体半径非常接近，而氧化态则与Bader方法非常接近。然而，当它们应用于电子产品时，只有BadELF算法产生具有化学意义的电荷。我们认为，BadELF方法提供了一种有用的策略来识别电子，并对它们最本质的性质--其中的电子数量--有了新的认识。
The selection and design of charge integration methods remain an outstanding challenge in materials chemistry. In complex materials like electrides, this challenge is amplified by the small charge and complex shape of electride wave functions. For these reasons, popular integration methods, such as the Bader method, usually fail to assign any charge to the bare electrons in an electride. To address this challenge, we developed an algorithm that instead partitions the charge based on the electron localization function (ELF), a popular scheme for visualizing chemically important features in molecules and solids. The algorithm uses Bader segmentation of the ELF to find the electride electrons and Voronoi segmentation of the ELF to identify atoms. We apply this method, “BadELF”, to the quantification of atomic radii and oxidation states in both ionic compounds and electrides. For ionic compounds, we find that the BadELF method yields radii that agree closely with Shannon crystal radii, while the oxidation states agree closely with the Bader method. When they are applied to electrides, however, only the BadELF algorithm yields chemically meaningful charges. We argue that the BadELF method provides a useful strategy to identify electrides and obtain new insight into their most essential property: the quantity of electrons within them.