【摘要】 使用混合密度泛函方法(MPW1PW91交换相关势),对Au3(HOC=NH)3分子进行了几何构型全优化,在此基础上构建了Au3(HOC=NH)3二聚体和三聚体模型,采用含时密度泛函方法研究了单体和低聚体模型的分子间Au-Au相互作用与其发光性质的关系.计算结果表明:此d10亚金化合物低能激发态的主要成分是反键或非键的Au(5d)电子轨道到前线附近Au(6p)空轨道的跃迁,并且这种激发大大加强了分子间Au-Au相互作用,从而形成激发多聚体,导致这类化合物溶液或固体发射谱红移.更多还原

【Abstract】 A full optimization on the ground-state geometry of the trinuclear gold(I) organometallic com- plex, Au3(HN=COH)3, was carried out at MPW1PW/SDD level. Some models of dimer and trimer of Au3(HN=COH)3 were set up basing on the optimized ground-state structure of the monomer. The lumines- cent properties and the intermolecular interactions of the oligomers of Au3(HN=COH)3 were studied by TD-DFT (time-dependent density functional theory) method. The results showed that the intermolecular aurophilic effects, which resulted in exciplexes, were strongly enhanced in the excited states and led to the huge red-shifts of the optical absorption and emission spectra. It also showed that the low energy transitions of these trigold complexes come mainly from occupied Au(5d) orbitals to vacant Au(6p) orbitals.更多还原