金属团簇的超原子分子理论  

The superatomic molecule theory of metal clusters

作　　者：刘立仁[1,2] 程龙玖 杨金龙[2] Liren Liu1,2, Longjiu Cheng3, Jinlong Yang2.(1 College of Physics and Electronic Engineering, Xinjiang Normal University, Urumqi 830054, China 2 Hefei National Laboratory for Physical Sciences at the Microscale and Synergetic, University of Science and Technology of China, Hefei 230026, China 3 School of Chemistry and Chemtcal Engtneering, Anhui University, Hefei 230601, Chin)

机构地区：[1]新疆师范大学物理与电子工程学院,乌鲁木齐830054 [2]中国科学技术大学合肥微尺度物质科学国家研究中心,合肥230026 [3]安徽大学化学化工学院,安徽230601

出　　处：《中国科学：化学》2018年第2期143-153,共11页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:21573001;21688102;21763024);国家重点基础研究发展计划(编号:2016YFA0200600);新疆师范大学博士科研启动基金(编号:XJNUBS1715);新疆矿物发光材料及微结构实验室(编号:FG1201)资助项目

摘　　要：选取合适的金属团簇(超原子)作为结构基元,进而组装形成新的团簇或晶体材料是团簇科学中一个有趣且充满挑战的课题,受到了实验和理论研究者的广泛关注.通过超原子组装这种"自下而上"的组装方式,可以获得具有特定物理化学性质的新材料.但是,长久以来针对如何进行超原子组装并无清晰、统一的理论认识,超原子组装基本等同于超原子的任意堆砌或拼接.那么,超原子能否像原子那样通过特定化学键形成分子或晶体?超原子间如何成键?超原子组装是否有一定模式可循?为了回答这些问题,我们提出了一个唯象理论:超原子分子理论.该理论的核心是构建超原子间的成键规则,将涉及超原子的"超级化学键"概括为3种类型,即超级共价键、超级杂化键和超级非键.超原子可以通过超级化学键结合形成超原子分子或超原子晶体.同时,超原子分子理论指出,超原子具有几何结构不同但电子结构相似的异构体,这些异构体称为"等同超原子".等同超原子同样可以作为组装基元,通过超级化学键进行结合.另外,针对包含复杂成键类型的团簇体系,超原子分子理论概括出了两种超原子组装模式,分别称为超原子网络和杂化超原子网络.综上所述,超原子分子理论包含了对超原子间成键规则的理解,对超原子组装基元的思考以及对超原子组装模式的认识.超原子分子理论的相关内容不仅可以为超原子组装提供系统的理论依据,而且可以对特殊团簇结构的稳定性给出合理解释,还可以为新型团簇的结构设计以及实验合成提供理论指导.Using special metal clusters（superatoms） as superatomic building blocks for hierarchically assembled materials allows these properties to be incorporated into designer materials with tailored properties. But how to assemble the superatoms to form materials is a critical problem, and no clear understanding until now. The assembly of the superatoms is basically equivalent to superatoms stacking. So, can superatoms, like atoms, form crystal by a particular chemical bond？ How to bond between superatoms？ Are there any strategy models for superatom assembly？ To answer those questions, a phenomenological theory named the superatomic molecule theory is introduced which contains understandings of the chemical bonds between superatoms, the building blocks and the assembly strategies. The chemical bonds between the superatoms can be classified into three types, including the super covalent bond, the super hybrid bond and the super non-bonding. A new perspective for the building blocks named isospueratom is introduced,which point out that the isomers of the superatoms can be chosen indiscriminately as building blocks. In addition to assembling superatoms by super valence bonds, other two superatom assembly strategies named superatom network and hybrid superatom network are included. In summary, the superatomic molecule theory contains the understanding of the bonds between superatoms, the thinking of the building blocks, and the consideration on strategies of the superatom assembly. The superatomic molecule theory cannot only be used as the theoretical basis of the superatom assembly, but also be used to understand the stabilities of some special cluster, and provides theoretical guidance for the new clusters design and synthesis.

关 键 词：金属团簇 化学键 超价键 超原子 超原子分子理论 

分 类 号：O641.4[理学—物理化学]