Application of Automated Reaction Path Search Methods to a Systematic Search of Single-Bond Activation Pathways Catalyzed by Small Metal Clusters: A Case Study on H-H Activation by Gold
Application of Automated Reaction Path Search Methods to a Systematic Search of Single-Bond Activation Pathways Catalyzed by Small Metal Clusters: A Case Study on H-H Activation by Gold
复制标题
自动反应路径搜索方法在小金属簇催化单键活化路径系统搜索中的应用：金H-H活化案例研究
DOI：
10.1021/ct500068b
复制
发表时间：
2014
影响因子：
5.5
通讯作者：
and Tetsuya Taketsugu
中科院分区：
文献类型：
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作者：
Min Gao;Andrey Lyalin;Satoshi Maeda;and Tetsuya Taketsugu
介绍了一种寻找金属簇催化的单键活化途径的新理论方法。所提出的方法结合了两种自动反应路径搜索技术：非谐向下失真跟踪（ADDF）和人工力诱导反应（AFIR）方法，在我们以前的工作中开发[Maeda，S.; Ohno，K.; Morokuma，K.Phys.Chem.Chem.Phys.2013，15，3683-3701]。以Aun（n= 7，8）团簇催化的H-H键活化的简单模型反应为例进行了讨论。我们分别在Au 7和Au 8团簇上自动找到了33个和20个H2解离的过渡态结构，并成功地确定了具有最低势垒的最佳解离途径.系统地分析了小团簇的结构依赖性反应性。它表明，最稳定的结构的金簇并不总是高度反应性和几个异构体的结构必须考虑在有限的温度下的反应速率的充分描述。所提出的方法可以作为一个有前途的工具，研究小金属簇催化的化学反应。
A new theoretical approach to find metal-cluster-catalyzed single bond activation pathways is introduced. The proposed approach combines two automated reaction path search techniques: the anharmonic downward distortion following (ADDF) and the artificial force induced reaction (AFIR) methods, developed in our previous works [Maeda, S.; Ohno, K.; Morokuma, K.Phys. Chem. Chem. Phys.2013,15, 3683–3701]. A simple model reaction of the H–H bond activation catalyzed by Aun(n= 7, 8) clusters is considered as an example. We have automatically found 33 and 20 transition-state (TS) structures for H2dissociation on Au7and Au8clusters, respectively, and successfully identified the best dissociation pathways with the lowest barrier. Systematic analysis of the structure-dependent reactivity of small gold clusters is performed. It is demonstrated that the most stable structures of the gold clusters are not always highly reactive and several isomeric structures must be taken into account for adequate description of the reaction rates at finite temperatures. The proposed approach can serve as a promising tool for investigation of the chemical reactions catalyzed by small metal clusters.