In homogeneous catalysis, the structure and electronic configuration of the active catalysts can vary significantly. Changes in ligation, oxidation, and spin states have the potential to influence the catalytic cycle energetics strongly that, to a large degree, dictate the catalytic performance. With the increased use of computational screening strategies aimed towards the identification of new catalysts, ambiguity surrounding structure/electronic configurations can be problematic, as it is unclear which species should be computed to determine a catalyst's properties. Here, we show that a single volcano plot constructed from linear free energy scaling relationships is able to account for variations in ligation, oxidation, and spin state. These linear scaling relationships can also be used to predict the free energies associated with a specific structure and electronic configuration of a catalyst based on a single descriptor. As a result, a single volcano plot can be used to screen prospective new catalysts rapidly.

中文翻译：

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关于分子火山图的一般性

在均相催化中，活性催化剂的结构和电子构型可以显着变化。连接，氧化和自旋状态的变化有可能强烈影响催化循环能，这在很大程度上决定了催化性能。随着旨在筛选新催化剂的计算筛选策略的使用增多，围绕结构/电子构型的含糊不清可能会成为问题，因为目前尚不清楚应该计算哪种物种来确定催化剂的性能。在这里，我们显示了由线性自由能比例关系构建的单个火山图能够解释结扎，氧化和自旋状态的变化。这些线性比例关系还可以用于基于单个描述符来预测与催化剂的特定结构和电子构型相关的自由能。结果，一个火山图可用于快速筛选潜在的新催化剂。