Gao Min, Lyalin Andrey, Maeda Satoshi, Taketsugu Tetsuya
Department of Chemistry, Faculty of Science, Hokkaido University , Sapporo 060-0810, Japan.
Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University , Kyoto 615-8245, Japan.
J Chem Theory Comput. 2014 Apr 8;10(4):1623-30. doi: 10.1021/ct500068b.
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 H2 dissociation on Au7 and Au8 clusters, 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.
介绍了一种寻找金属簇催化单键活化途径的新理论方法。该方法结合了两种自动反应路径搜索技术：非谐向下畸变跟踪（ADDF）和人工力诱导反应（AFIR）方法，这两种方法是我们之前的工作中开发的[前田，S.；大野，K.；森口，K.《物理化学化学物理》2013年，15，3683 - 3701]。以Aun（n = 7, 8）簇催化的H - H键活化的简单模型反应为例。我们分别自动找到了在Au7和Au8簇上H2解离的33个和20个过渡态（TS）结构，并成功确定了具有最低势垒的最佳解离途径。对小金簇的结构依赖性反应性进行了系统分析。结果表明，金簇最稳定的结构并不总是具有高反应活性，在有限温度下充分描述反应速率时必须考虑几种异构体结构。所提出的方法可作为研究小金属簇催化化学反应的一种有前途的工具。
