A descriptor of “material genes”: Effective atomic size in structural unit of ionic crystals

The atomic size of each element, described by the ionic radius, is one category of “material genes” and can facilitate our understanding of atomic arrangements in compounds. Most of the ionic radii currently used to measure the sizes of cations and anions in ionic crystals are derived from hard-sphere model based on the coordination numbers, or the soft-sphere model incorporating the effect of ionic polarization. Herein we take a first step towards a novel “effective atomic size” (EAS) model, which takes into consideration the impact of the types and number of neighboring atoms on the relationship between ionic radii and interatomic distances. Taking the binary compounds between Group IA/IIA and VIA/VIIA elements gathered from the latest databases as an example, we show that the proposed EAS model can yield excellent agreement between the predicted and the DFT-calculated interatomic distances, with deviation of less than 0.1 Å. A set of EAS radii for ionic crystals has been compiled and the role of coordination numbers, geometric symmetry and distortion of structural units has been examined. Thanks to its superior predictability, the EAS model can serve as a foundation to analyze the structure of newly-discovered compounds and to accelerate materials screening processes in the future works.

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