In a previous paper [M. Dittner and B. Hartke, J. Chem. Theory Comput. 14, 3547 (2018)], we introduced a preliminary version of our GOCAT (globally optimal catalyst) concept in which electrostatic catalysts are designed for arbitrary reactions by global optimization of distributed point charges that surround the reaction. In this first version, a pre-defined reaction path was kept fixed. This unrealistic assumption allowed for only small catalytic effects. In the present work, we extend our GOCAT framework by a sophisticated and robust on-the-fly reaction path optimization, plus further concomitant algorithm adaptions. This allows smaller and larger excursions from a pre-defined reaction path under the influence of the GOCAT point-charge surrounding, all the way to drastic mechanistic changes. In contrast to the restricted first GOCAT version, this new version is able to address real-life catalysis. We demonstrate this by applying it to the electrostatic catalysis of a prototypical Diels–Alder reaction. Without using any prior information, this procedure re-discovers theoretically and experimentally established features of electrostatic catalysis of this very reaction, including a field-dependent transition from the synchronous, concerted textbook mechanism to a zwitterionic two-step mechanism, and diastereomeric discrimination by suitable electric field components.

中文翻译：

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Diels-Alder反应的全球最佳催化场

在以前的论文中[M. Dittner和B.Hartke，化学杂志。理论计算。14，3547（2018）]，我们介绍了GOCAT（全球最佳催化剂）概念的初步版本，其中通过对反应周围的分布点电荷进行全局优化，为任意反应设计了静电催化剂。在第一个版本中，预定义的反应路径保持不变。这种不切实际的假设仅允许很小的催化作用。在当前的工作中，我们通过复杂而健壮的动态反应路径优化以及其他伴随的算法调整扩展了GOCAT框架。这允许在GOCAT点电荷周围的影响下，从预定的反应路径进行越来越小的偏移，一直到剧烈的机械变化。与受限制的第一个GOCAT版本相反，该新版本能够解决现实生活中的催化问题。我们通过将其应用于原型Diels-Alder反应的静电催化来证明这一点。在不使用任何先验信息的情况下，该程序重新发现了该反应的静电催化的理论和实验确定的特征，包括从同步一致的教科书机制到两性离子两步机制的场相关转变，以及通过适当的对映异构鉴别电场分量。