【摘要】 用从头算方法研究 [Au( i-mnt) ]2 - 2 ( i-mnt=i-marononitriledithiolate)的电子吸收和磷光发射性质 ,利用MP2和 CIS方法分别优化了 [Au( i-mnt) ]2 - 2 基态和激发态几何结构 .计算的基态 Au( )— Au( )键长为0 .2 82 5 nm,表明 Au( )之间存在弱吸引作用 .采用 SCRF方法中 IPCM模型模拟配合物在乙氰溶液中的行为 ,计算得到的最大吸收波长为 31 5 .5 nm,指认 X1 Ag→ A1 Au 来源于 i-mnt配体内电荷转移跃迁 .在 4 36 .2 nm处得到具有 B3 Au→ 1 Ag 跃迁的磷光发射 ,指认为 i-mnt配体内电荷转移和金属到配体电荷转移跃迁 ,与5 0 0 nm乙氰溶液的发射相对应 ,为金属修饰的有机配体发光机制 .更多还原

【Abstract】 The structures of 2- 2 (i-mnt=i-marononitriledithiolate) were optimized by the ab initio MP2 and CIS methods for the ground state and excited state respectively. The calculated ground-state Au(Ⅰ)-Au(Ⅰ) distance of 0.282 5 nm indicates a weak attraction between the two metallic Au(Ⅰ) atoms. The IPCM(Isodensity Polarized Continuum Model) approach in the SCRF (Self-Consistent Reaction Field) method was employed to account for the solvent effect of the acetonitrile solvent, and the electronic structures, electronic absorption and emission of 2- 2 in acetonitrile were obtained by the CIS calculations. The calculated absorption maximum, 315.5 nm, with the oscillator strength of 1.391 is assigned as an intraligand charge transfer(ILCT) transition. The phosphorescence with the wavelength of 436.2 nm arising from B 3A u→ 1A g is attributed to ILCT and metal to ligand charge transfer (MLCT) transitions, comparable to the emissive band around 500 nm of 2 2 in glass acetonitrile solution at 20 K in the experiment. Such a transition is described as an organ-ligand luminescent mechanism with metal decoration.更多还原