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分子水平上的激发态理论研究能够用来解释分子材料的多色发光机理.采用单组态相互作用方法,计算研究了四种二配位的Au(I)配合物Ph3PAuCl,Ph3PAuBr,Ph3AsAuCl和Ph3AsAuBr的分子结构限制的三重激发态(T1a)和分子结构松弛的三重激发态(T1b)的分子结构与光物理性质.由于θ(PAuX)/θ(AsAuX)从180°扭曲到120°左右,T1b态的能量在单线态组态相互作用(CIS)水平上降低了0.805-1.124eV,在密度泛函理论(DFT)水平上降低了0.820-0.947eV.自然键轨道电荷布居数分析表明,在T1a态中两个单电子主要分布在一个苯基上,而在T1b态中两个单电子分布在PAuX/AsAuX上.因此,在晶体中观察到的较高能磷光归属于T1a态的苯基之间的3π*→1π电子跃迁,而较低能磷光主要起源于T1b态的Au的3σ*→1σ电子跃迁.
The theoretical study of the excited state at the molecular level can be used to explain the multicolor luminescence mechanism of molecular materials. The four kinds of coordination complexes of Au (I) Ph3PAuCl, Ph3PAuBr, Ph3AsAuCl and Ph3AsAuBr (T1a) of the molecular structure and the triplet excited state (T1b) of the molecular structure.The molecular structure and photophysical properties of T1b due to the twist of θ (PAuX) / θ (AsAuX) from 180 ° to 120 ° State energy decreased by 0.805-1.124eV at the level of singlet interaction (CIS) and decreased by 0.820-0.947eV at the level of density functional theory (DFT). The analysis of the population of natural bond orbital charge showed that at In the T1a state, two single electrons are mainly distributed on one phenyl group, while in the T1b state two single electrons are distributed on the PAuX / AsAuX. Therefore, the higher energy phosphorescence observed in the crystal is attributable to the phenyl group in the T1a state 3π * → 1π electron transitions, whereas the lower energy phosphorescence mainly originates from the 3σ * → 1σ electron transition of the T1b state Au.