1,3-二氮杂薁类衍生物电子结构和光谱性质的理论研究

Theoretical Studies on Electronic Structures and Spectroscopic Properties of 1,3-Diazaazulene Derivatives

对1,3-二氮杂薁类衍生物采用密度泛函理论(DFT)在B3LYP/6-31G(d)的水平上进行了几何构型的全优化,在此基础上探讨了分子结构和前线分子轨道能量等性质的变化规律,采用含时密度泛函理论(TD-DFT)计算了分子的电子跃迁性质,采用二维平面图和三维立体图来直观表示激发态的性质,研究分子内电子转移特性.跃迁密度矩阵的二维等高线图反映了电子-空穴相干性,三维跃迁密度图反映了跃迁偶极矩的方向和强度,三维电荷差异密度图说明了激发过程中分子内电子转移性质.

The geometries of four different kinds of 1,3-diazaazulene derivatives were fully optimized with Density Function Theory（DFT） at B3LYP/6-31G（d） level, on basis of which the energies of frontier molecular orbitals and the energy gap were investigated and the electronic transition properties were calculated with time-dependent DFT（TD-DFT） at the same level. The excited-state properties and the intra-molecular charge transfer（ICT） character were investigated with the two-dimensional （2D） and three-dimensional （3D） real space analysis methods. The electron-hole coherence is investigated with 2D contour plots of transition density matrix. The orientation and strengths of absorptive transition dipole moment are obtained by 3 D transition density（TD）. The ICT orientations are obtained with 3D charge difference density（CDD）.