【作者】 卜新平；

【导师】 仲崇立；

【作者基本信息】 北京化工大学 ， 化学工程， 2005， 博士

【摘要】 在气相单分子或原子与凝聚态物质之间，团簇起着桥梁的作用，它能解释诸如成核现象、相变、溶剂化以及簇的特殊反应。团簇中原子—原子或者离子—原子间的相互作用机理成为许多实验和理论研究的主题。金属有机骨架材料是一种类似于沸石的软材料，但是它具有所有含碳化合物的化学多样性。并具有较大的表面积和孔隙率，以及特定尺寸的可裁剪性，高渗透性等特性，正好满足催化、分离、能量储存与释放的需要。开发其在吸附剂和膜分离材料的应用，对环境和能源工程具有非常重要的实际意义。计算化学（包括分子模拟与量子化学）不仅可以突破传统方法中的局限性，而且还可为最佳吸附材料的设计和最优操作工况的确定提供理论依据，通过对材料与客体分子间相互作用的研究，能够对材料微相结构与性能进行控制，材料的制备将实现从以经验为主向定量、定向制备的转变，从而节省大量繁杂的实验研究。 本论文对于金属离子—氦原子团簇主要采用量子化学从头计算的方法，研究了分子结构和成簇机理。对于金属有机骨架材料储能和吸附性能采用基于量子化学和分子模拟两种方法，构建了多个计算模型，并进行了系统的研究。基于上述研究方法，主要内容和创新点如下： 对Be⁺He_n（n=1-12），Mg⁺He_n（n=1-10）和Mg²⁺He_n（n=1-10）离子团簇采用GAUSSIAN03软件进行了量子化学从头计算，得到其最稳定结构，以及相应的经ZPE（零点振动能校正）和BSSE（基组重叠误差）校正后的结合能，以及离子团簇的振动频率，分析了多体作用和基组重叠误差对结合能的影响。BeHe_n⁺（n=1-10）和MgHe_n⁺（n=1-10）离子团簇可用溶解态模型描述，从一侧逐渐包围带电离子到最后排满第一壳层。而Mg²⁺He_n（n=1-10）离子团簇具有更高的对称性，二价镁离子总被氦原子包围于中心。Be⁺He_n，Mg⁺He_n，Mg²⁺He_n离子团簇第一壳层充满氦原子数目分别为12，20，9，后两者结果与实验观测值吻合。更多还原

【Abstract】 Complexes act as the linker between the molecule or atom and the condensed material. It helps to understand the nucleation phenomena, phase transitions, solvation and cluster specific reactions. The investigations of the interactions of atom-atom and ion-atom are the subjects of many experimental and theoretical researches. Metal-organic framework materials are analogues of zeolites, but with all of the chemical diversity. The researches of this new class of materials are trying to develop adsorbents and membranes that will revolutionize small-molecule sperations, as well as new kinds of catalysts with good permeability, high void volumes, and well defined tailorable cavities of uniform for gas separations and storage/release applications. It is very important to environmental and energy engineering. Computational chemistry, including molecular simulation and quantum chemistry, can not only overcome the limitations of traditional methods, but also provide theoretical guidance for the design of optimal adsorbents and the determinations of optimal industrial operations. The control over the structure and design of new material with specific characteristic can be completed by the studies of interaction between sorbent and adsorbent. It saves a lot of time for complicated experimental works.In this work, quantum chemistry calculations of the structure and the forming mechanism of metal ion-helium complexes are carried out, Research of energy storage and adsorption by use of metal-organic framework-5 have been done with quantum chemistry calculation and molecular simulations. The main contents and findings are summarized as follow.Firstly, Ab initio quantum chemistry calculations of Be⁺He_n （n=1-12）, Mg⁺He_n （n=l-10） and Mg²⁺He_n （n=1-10） complexes are performed using GAUSSIAN03 software package. The most stable structures and the binding energy corrected by ZPE更多还原