Elucidation of Reaction Mechanism with the Unified Reaction Valley Approach: Part III Homogeneous Catalysis and Beyond

凭借这一奖项，化学结构、动力学和机理（CSDM-B）和计算与数据驱动科学与工程（CDS&amp；E）项目支持南卫理公会大学的Elfi Kraka和Dieter Cremer教授推导出结合均相和酶催化特性的下一代化学催化剂的一般设计原则。Cremer和Kraka的统一反应谷方法（unified reaction valley approach， URVA）旨在作为一种量子化学工具，在比目前容易达到的更高水平上研究催化反应的机理。URVA就像一个附着在反应复合物上的“高分辨率相机”，能够揭示振动与反应复合物电子结构变化之间的相互作用。它记录了反应络合物沿着反应侧的能量谷向上到达能量通过点，然后向下通过出口谷到达产物的所有事件。通过分析反应路径的方向和曲率来区分重要和不重要的事件，而不是反应配合物本身的特征。用这种方法可以确定催化反应和非催化反应之间的基本区别，但人造催化剂的局限性也很明显。酶是为应对严峻的生存压力而发展起来的调谐良好的催化剂。鉴于许多酶具有显著的催化能力，主要的重点将放在URVA方法在酶催化中的扩展和应用上，以确定其主要优势。系统地分析和比较过渡金属、非过渡金属或无金属和（人工）酶催化反应的机理。将制定一项重新设计催化剂的战略，其中包括化学和生物催化的各个方面，可以作为加强跨学科努力的孵化器，以产生特定目标的催化剂。所有被调查的反应（包括反应电影）的数据将被收集到CATCO反应库中，该反应库将增加到500多个反应。该图书馆将提供给化学社区的研究，教学和学生培训。在过去的两年中，URVA已被证明是一种独特的工具，用于150多种均相催化反应的机理研究。除了跟踪键断裂和形成的化学过程外，URVA还使用了一种经过大幅改进的算法，用于跟踪远至范德瓦尔斯区域的反应谷，以高度详细地监测化学前和化学后的过程。根据内部坐标或曲线坐标分量分析反应谷的方向和曲率，然后直接与电子结构变化相关。URVA的其他重要工具是局部振动模式分析、电荷转移和电荷极化分析以及用反应相表示化学反应。方法开发将包括以下方面的设计和编程：i)用于隐式或显式包含溶剂效应的URVA方法，ii)用于研究“相对论性”系统的2组分相对论方法，以及iii)用于描述酶促环境中化学反应的新的QM/MM方法。

With this award, the Chemical Structure, Dynamics and Mechanism (CSDM-B) and Computational and Data-Enabled Science and Engineering (CDS&E) programs are supporting Professors Elfi Kraka and Dieter Cremer at Southern Methodist University to derive a general design principle for the next generation of chemical catalysts combining features of homogenous and enzyme catalysis. The unified reaction valley approach (URVA) of Cremer and Kraka aims to serve as a quantum chemical tool to study the mechanism of catalyzed reactions at a greater level of than is currently easily achieved. URVA acts like a "high-resolution-camera" attached to the reaction complex, being able to reveal the interplay between vibrations and the electronic structure changes of the reaction complex. It records all events when the reaction complex follows the energy valley on the reaction side up to the energy pass point and then down through the exit valley to the products. Important and less important events are differentiated by analyzing direction and curvature of the reaction path rather than features of the reaction complex itself. Basic differences between and catalyzed and non-catalyzed reactions can be determined in this way, but also the limitations of man-made catalysts are apparent. Enzymes are the well-tuned catalysts developed in response to stringent survival pressures. Given the remarkable catalytic power seen in many enzymes, the major focus will be on the extension and application of the URVA methodology to enzyme catalysis to determine its major advantages. The mechanism of transition metal, non-transition metal or metal-free- and (artificial) enzyme-catalyzed reactions will be systematically analyzed and compared. A strategy for de novo catalyst design is to be developed, which, by including aspects of both chemo- and bio-catalysis, can serve as an incubator for enhanced interdisciplinary efforts to generate target-specific catalysts. The data of all reactions investigated (including reaction movies) will be collected in the CATCO reaction library, which will increase to more than 500 reactions. This library will be available to the chemical community for research, teaching, and student training.During the past two years, URVA has proven to be a unique tool for the mechanistic study of more than 150 homogenous catalysis reactions. In addition to following the chemical processes of bond breaking and forming, URVA uses a substantially improved algorithm for following the reaction valley far out into the van der Waals region to monitor pre- and post-chemical processes in a high level of detail. The direction and curvature of the reaction valley are analyzed in terms of internal coordinate or curvilinear coordinate components and then directly related to electronic structure changes. Other essential tools of URVA are the local vibrational mode analysis, the charge transfer and charge polarization analysis as well as the presentation of the chemical reaction in terms of reaction phases. Method development will include the design and programming of i) URVA methodologies for an implicit or explicit inclusion of solvent effects, ii) 2-component relativistic methods for the investigation of "relativistic" systems, and iii) new QM/MM methodologies for the description of chemical reactions in an enzymatic environment.