Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Inorg Chem. 2011 Jan 17;50(2):656-63. doi: 10.1021/ic102031h. Epub 2010 Dec 13.
The existence of new compounds is often postulated by solid state chemists by replacing an ion in the crystal structure of a known compound by a chemically similar ion. In this work, we present how this new compound discovery process through ionic substitutions can be formulated in a mathematical framework. We propose a probabilistic model assessing the likelihood for ionic species to substitute for each other while retaining the crystal structure. This model is trained on an experimental database of crystal structures, and can be used to quantitatively suggest novel compounds and their structures. The predictive power of the model is demonstrated using cross-validation on quaternary ionic compounds. The different substitution rules embedded in the model are analyzed and compared to some of the traditional rules used by solid state chemists to propose new compounds (e.g., ionic size).
固态化学家通常通过用化学性质相似的离子取代已知化合物晶体结构中的离子来假设新化合物的存在。在这项工作中，我们提出了如何通过离子取代将这种新化合物的发现过程表述在一个数学框架中。我们提出了一个概率模型，评估离子物种相互取代的可能性，同时保持晶体结构。该模型在晶体结构的实验数据库上进行训练，可以用于定量地提出新的化合物及其结构。通过对四元离子化合物的交叉验证，证明了该模型的预测能力。分析了模型中嵌入的不同取代规则，并将其与固态化学家用于提出新化合物的一些传统规则（例如离子大小）进行了比较。
