非金属小团簇成键特征与光电功能分子设计的理论研究

项目名称： 非金属小团簇成键特征与光电功能分子设计的理论研究

项目编号： No.21473088

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 刘春根

作者单位： 南京大学

项目金额： 80万元

中文摘要： 本项目针对B、C元素所形成的小型高对称性团簇，通过运用高精度从头计算法研究小团簇稳定性的电子结构本质化与学成键图像，探寻使小团簇稳定化的结构调变途径；结合反应过渡态理论与非绝热动力学模拟，研究热化学、电化学、光化学等条件下,团簇的结构转变机制与动力学行为特征。基于小团簇性质的系统分析，结合密度泛函理论与半经验量子化学模型方法，研究从单体、二聚体，直至更高聚合度寡聚物的电子结构与稳定性的变化与聚合度、拓扑连接方式等结构因素的相互关系；研究基态与激发态条件下相邻团簇单元间电子（电荷）转移与能量转移过程的微观机理，为探讨小团簇组装在功能分子设计方面可能存在的实际意义提供有参考价值的理论信息。

中文关键词： 量子化学计算；电子激发态；分子动力学模拟；电子结构；反应机理

英文摘要： This project will focus on the studies of small while highly symmetric boron and carbon atomic clusters. High-level ab initio methods will be employed to reveal the nature of chemical bonding in such kind of small clusters, which might be essential for the understanding of the substituent effect on their chemical stabilities. Transition state theories and non-adiabatic dynamics simulations will be performed to investigate the thermal, electrochemical and photochemical isomerizations of these small clusters. Further molecular design based on the assembly of the small clusters toward novel opto-eletronic functions will also be involved after systematical investigations on chemical and electronic properties of small to large oligomers, as well as their relationship with the degree of polymerization and connection topology among monomers. New semiempirical quantum chemical methods will be developed, which will be used together with density functional theories, to investigate the electron (charge) and energy transfer behaviors among neighboring cluster moieties in oligomers, both in ground and in excited states.

英文关键词： Multi-reference quantum chemistry computation;Excited electronic state;Non-adiabatic dynamics simulation;Chemical bonding in small non-metallic clusters;Photochemical reaction mechanism