三联吡啶铂(Ⅱ)配合物光谱性质的密度泛函研究

采用密度泛函理论方法(DFT),对三联吡啶铂(Ⅱ)配合物的结构与电子光谱进行了系统研究.筛选的PBE/LanL2DZ(6-311+G(d))—BMK/LanL2DZ(6-31+G(d))方法,计算结果能较好地与实验值吻合:对光谱峰波长的计算,吸收光谱和发射光谱平均误差分别为14 nm和17 nm.通过对前线分子轨道的分析,归属了各光谱峰的跃迁类型.计算结果表明,不同推拉电子效应的取代基对配合物光谱峰的位置和跃迁类型具有较大影响,为已有的实验结论提供了有力的理论阐述.

DFT Studies on the Spectroscopic Properties of Terpyridine Pt(II) Complexes

The structures and electronic spectra of terpyridine platinum(Ⅱ) complexes were studied systematically with density functional theory.The results of selected PBE/LanL2DZ(6-311+G(d))—BMK/LanL2DZ(6-31+G(d)) method are in good agreement with experimental values: the average inaccuracy of wavelength calculation in absorption and emission spectra are 14 nm and 17 nm,respectively.The spectra peaks were all assigned via analyzing the frontier molecular orbits.The calculation results reveal that different electron donating or withdrawing groups influence spectral peaks' positions and transition types crucially,and provide strong theoretical understandings for existing experimental results.