Center for Materials Crystallography, Department of Chemistry and iNANO, Aarhus University, Langelandsgade 140, 8000, Aarhus C, Denmark.
Chemistry. 2019 Nov 27;25(66):15010-15029. doi: 10.1002/chem.201903087. Epub 2019 Sep 18.
Rational material design requires a deep understanding about the relationship between the structure and properties of materials, which are both intimately related to their chemical bonding. Through the experimentally observable electron density, chemical bonding can be understood from experimental and theoretical points of view on an equal footing, and advances in accurate X-ray diffraction measurements and computational techniques over the past decades have provided access to electron density distributions in increasingly complex functional materials. In this Review, selected electron density studies from the literature on a wide range of materials classes are presented, including studies of thermoelectric materials, high pressure electrides, coordination polymers and non-linear optical materials. These studies demonstrate how detailed analysis of chemical bonding based on the electron density provides important understanding of materials beyond arguments based on structure and simple chemical concepts. In cases such as understanding the conducting properties of Zintl semiconductors or the effect of mutual electrical polarization in host-guest systems, it is clearly imperative to go beyond structure and examine the chemical bonding in detail. In the Review, the complementarity between theory and experiment is underlined, which allows for mutual validation of new chemical bonding concepts, and indeed experiment and theory may challenge each other based on the different strengths and weaknesses of each method.
理性的材料设计需要深入了解材料的结构和性能之间的关系，而这两者都与它们的化学成键密切相关。通过实验可观测的电子密度，可以从实验和理论两个方面平等地理解化学成键，过去几十年来，精确的 X 射线衍射测量和计算技术的进步使得越来越复杂的功能材料的电子密度分布能够被获取。在这篇综述中，展示了来自广泛材料类别的文献中的一些电子密度研究，包括热电材料、高压电化物、配位聚合物和非线性光学材料的研究。这些研究表明，基于电子密度的化学成键的详细分析如何为材料提供了除基于结构和简单化学概念的论点之外的重要理解。在某些情况下，例如理解 Zintl 半导体的导电性质或主客体体系中相互电极化的影响，超越结构并详细检查化学成键显然是必要的。在综述中，强调了理论和实验之间的互补性，这允许新的化学成键概念的相互验证，实际上，实验和理论可能会根据每种方法的不同优势和弱点相互挑战。
