三联吡啶铂(Ⅱ)配合物光谱性质的密度泛函研究

doi:10.7517/j.issn.1674-0475.2010.06.433

影像科学与光化学 ›› 2010, Vol. 28 ›› Issue (6): 433-441.DOI: 10.7517/j.issn.1674-0475.2010.06.433

三联吡啶铂(Ⅱ)配合物光谱性质的密度泛函研究

李立^1,2, 吕小军¹, 迟绍明³, 傅文甫^1,3

1. 中国科学院, 理化技术研究所, 北京, 100190;
2. 中国科学院, 研究生院, 北京, 100049;
3. 云南师范大学, 化学化工学院, 云南, 昆明, 650092

收稿日期:2010-06-04 修回日期:2010-06-23 出版日期:2010-11-23 发布日期:2010-11-23
通讯作者: 傅文甫

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

LI Li^1,2, LÜ Xiao-jun¹, CHI Shao-ming³, FU Wen-fu^1,3

1. Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P.R.China;
2. Graduate University of Chinese Academy of Sciences, Beijing 100049, P.R.China;
3. College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, Yunnan, P.R.China

Received:2010-06-04 Revised:2010-06-23 Online:2010-11-23 Published:2010-11-23

摘要/Abstract

摘要： 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.

关键词: 三联吡啶铂配合物, 电子光谱, 激发态, 电荷转移跃迁, 密度泛函理论

Abstract: 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.

Key words: terpyridine platinum complex, electronic spectra, excited state, charge transfer transition, density functional theory

中图分类号:

O614

李立, 吕小军, 迟绍明, 傅文甫. 三联吡啶铂(Ⅱ)配合物光谱性质的密度泛函研究[J]. 影像科学与光化学, 2010, 28(6): 433-441.

LI Li, LÜ Xiao-jun, CHI Shao-ming, FU Wen-fu. DFT Studies on the Spectroscopic Properties of Terpyridine Pt(Ⅱ) Complexes[J]. Imaging Science and Photochemistry, 2010, 28(6): 433-441.

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三联吡啶铂(Ⅱ)配合物光谱性质的密度泛函研究

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

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