含氩原子的水合二价铜离子团簇结构和振动光谱的理论研究

Water and hydrated divalent copper ions clusters are closely related to many modern front works containing biology and medicine. The study of structures and function is an interdisciplinary project, which not only has high academic value but also has broad application prospects. The geometrical structures, electronic properties, energies, bond energies and dissociation energies are studied using high-order dynamic electron correlation method of molecular orbital theory. The nature of weak interaction among water molecules in water clusters as well as between water cluster and other ion are expored using molecular interaction potential energy surface models, which reveals the mechanism of hydrogen-bonded molecular. The stability in water and hydrated ions clusters as well as the factors influencing the stability including the dependence of polarity, cluster on size are also explored. The studies can deepen the understanding of water clusters and hydrated ion clusters and can tap their potential application background as well as explain experimental new results and new phenomena in theory. The studies also can new value structure and characteristics of cluster compounds, which provide theoretical basis for applications and synthesis in the experiments. In particular, they can give the nature of hydrogen bonds, nature, mechanism, the mechanism of the formation, as well as the theory describing hydrogen bonds models, which reveals the mechanism of hydrogen-bonded molecular. The stability in water and hydrated noble metal ions clusters as well as the factors influencing the stability including the dependence of polarity, cluster on size are also explored. The studies can deepen the understanding of water clusters and hydrated ion clusters and can tap their potential application background as well as explain experimental new results and new phenomena in theory. The studies also can new value structure and characteristics of cluster compounds, which provide theoretical basis for applications and synthesis in the experiments. In particular, they can give the nature of hydrogen bonds, nature, mechanism, the mechanism of the formation, as well as the theory describing hydrogen bonds.

水团簇及水合二价铜离子团簇与生物、医学等诸多近代前沿工程密切相关，其结构与功能的研究是一个多学科交叉课题，不仅具有极高的学术价值，而且具有广泛的应用前景。本申请在分子轨道理论框架下，使用高阶动态电子相关方法，研究水团簇及水合离子团簇的几何结构和电子性质、能量、键能和离解能等；使用分子之间相互作用势能面模型，探索在水团簇内水分子之间以及水团簇与其它离子之间弱相互作用的本质，揭示氢键分子的成键机理；探索水团簇及水合离子团簇的稳定性，以及探索影响团簇稳定性的因素，包括离子的极性、团簇对尺寸的依赖性等。这些研究能加深对水团簇及水合离子团簇的了解和认识，能挖掘它们潜在的应用背景，能从理论上解释实验的新结果和新现象, 并能预言新的有价值的水团簇化合物的结构和特性，为实验上合成和应用它们提供理论依据。特别是能给出关于氢键的本质、性质、形成的机理、作用机理、以及描写氢键的理论。

本课题采用从头算方法对水合二价铜离子团簇进行了研究，研究表明水合二价铜离子团簇的相互作用能大于单个红外光子的能量，要使水合二价铜离子团簇有效解离从而获得单光子红外光解光谱，需要借助“加入氩原子”的技术。项目进而对含氩原子的水合二价铜离子团簇的几何结构，相互作用能和红外光谱进行了研究，研究发现：（1）Ar原子既可以与二价铜离子结合，又可以与H原子相连。Ar原子的不同结合位置导致含氩原子的水合二价铜离子团簇有多个异构体结构。（2）对于Cu2+(H2O)团簇，需要通过加入四个Ar原子的方法来使Cu2+(H2O)有效解离。复合物Cu2+(H2O)Ar4中Ar原子与Cu2+(H2O)间的结合能小于一个红外光子的能量，加入Ar原子的团簇共振吸收单个红外光子后，通过团簇内部振动再分布过程将结合力最弱的Ar原子解离掉从而获得Cu2+(H2O)的单光子红外解离光谱。（3）对于Cu2+(H2O)2团簇，在加入三个Ar原子后形成的复合物Cu2+(H2O)2Ar3中，单个红外光子可以解离掉一个Ar原子进而得到Cu2+(H2O)2的红外光解光谱。（4）Ar原子的引入会对复合物造成一定的扰动。若Ar原子与Cu2+相结合，Ar原子与Cu2+的相互作用使OH键缩短，OH伸缩频率增大，导致红外光谱发生蓝移现象，而Ar原子与H2O中的H原子相连使相应的OH键伸长，红外光谱发生红移现象。对含氩原子的水合二价铜离子团簇的详细研究，从理论上分析能否通过加入惰性气体原子方法获得水合二价铜离子团簇的红外光谱，为实验上合成和应用水合二价铜离子团簇提供重要的理论依据。