配体场效应下典型超原子簇及其组装材料的结构与功能调控的机制研究

本课题拟开展的研究内容契合重大研究计划中团簇的电子结构及演化规律这一重点资助方向。气相和凝聚相团簇研究是团簇科学领域的两大重要分支。凝聚相中，以功能为导向的多级团簇结构的精准设计合成是亟待解决的难题。将气相中较成熟的理论及模型扩展至复杂的凝聚相中，构建联结气相和凝聚相研究的桥梁具有重要意义。本项目拟利用第一性原理理论计算并辅以飞行时间质谱-光电子速度成像能谱(TOF-VMI)实验技术，以典型的主族和过渡金属超原子簇为研究对象，深入理解气相以及凝聚相中不同配体场效应对超原子簇及其团簇组装材料的结构演化规律、化学成键、稳定性、电子性质及构效关系的调控规律和本质。通过对具有不同类型价电子及壳层结构的超原子簇模型体系的研究，进一步理解轨道对称性和电子结构在配体化过程中对成键、配体化动力学等的作用与机制。本项目可为凝聚相中以功能为导向的团簇组装材料的定向合成提供有效的理论模型和依据。

The research content of the present project belongs to the key funding field of the electronic structure and evolution rule of clusters of the current Major Research Plan of the National Natural Science Foundation of China. Gas-phase and condensed-phase studies are two important research areas in cluster science. In the condensed-phase, the precise design and synthesis of hierarchical structures of clusters featuring specific functions is a long-standing puzzle. Thus, bridging the gap between the gas-phase and condensed-phase and extending the well-known fundamental theory and models in the gas-phase to the condensed-phase are of great significance. In this project, by employing the first-principle theoretical calculations and time-of-flight (TOF) coupled photoelectron imaging spectroscopic technique, the ligand field effect on typical superatoms of main and transition group elements will be explored. Specifically, we will focus on the regulation role and mechanism of the ligands used in the condensed-phase syntheses on the structural evolution, chemical bonding, stability, electronic properties, and structure-activity relationship of superatoms and their assembled nanomaterials. Meanwhile, the theoretical and experimental investigations on the superatoms featuring different types of valence electrons and shell configurations will enable us to get a deeper insight about the role of the orbital symmetry on the chemical bonding and dynamics in the ligation process. This project could provide effective theoretical model and valuable information about the precise syntheses of cluster assembly materials with specific functions in the condensed phase.