位移谐振子模型对三(2-苯基吡啶)合铱磷光光谱影响的理论研究

引用本文: 王晓峰, 左国防, 李志锋, 李会学. 位移谐振子模型对三(2-苯基吡啶)合铱磷光光谱影响的理论研究[J]. 物理化学学报, 2015, 31(9): 1667-1676. doi: 10.3866/PKU.WHXB201507092 shu

Citation: WANG Xiao-Feng, ZUO Guo-Fang, LI Zhi-Feng, LI Hui-Xue. Theoretical Study of the Phosphorescence Spectrum of Tris(2-phenylpyridine)iridium Using the Displaced Harmonic Oscillator Model[J]. Acta Physico-Chimica Sinica, 2015, 31(9): 1667-1676. doi: 10.3866/PKU.WHXB201507092 shu

位移谐振子模型对三(2-苯基吡啶)合铱磷光光谱影响的理论研究

基金项目:
国家自然科学基金(21465021, 21463023) (21465021, 21463023)

教育部重点项目(211189) (211189)

甘肃省自然科学基金(1208RJZE139) (1208RJZE139)

甘肃省高校领军人才项目(11zx-04) (11zx-04)

天水师范学院重点学科项目资助

摘要:

采用谐振子模型理论探讨了振动模式对Ir(ppy)₃配合物的磷光光谱的影响. 多原子分子发射光谱的一般形式可以从两个绝热电子态之间的热振动关联函数推导出, 相应地势能面之间的位移和Duschinsky转动的影响也被包含在多维谐振子模型的表达式中, 所得关系式模拟出了Ir(ppy)₃较为精细的磷光发射光谱. 计算结果表明T₁态到S₀态之间的0→1振动跃迁对发射光谱贡献较大, 尤其振动频率小于1600 cm^-1的振动模贡献更多, 配体中苯和吡啶环上C=C和C=N的呼吸振动, 是Ir(ppy)₃出现肩峰的主要原因. 玻耳兹曼分布使得主峰和肩峰的强度下降, 并且两峰相互接近. 该谐振子模型与密度泛函理论(DFT)结合, 可以较好地定量描述多原子分子光物理过程的发射光谱以及详细了解光谱谱图的细节.

关键词:

English

Theoretical Study of the Phosphorescence Spectrum of Tris(2-phenylpyridine)iridium Using the Displaced Harmonic Oscillator Model

1.
College of Chemical Engineering and Technology, Tianshui Normal University, Tianshui 741001, Gansu Province, P. R. China
Received Date: 07 May 2015
Available Online: 06 September 2015
Fund Project:
国家自然科学基金(21465021, 21463023)

教育部重点项目(211189)

甘肃省自然科学基金(1208RJZE139)

甘肃省高校领军人才项目(11zx-04)

天水师范学院重点学科项目资助

Abstract:

We present a comprehensive investigation of the phosphorescence spectrum of Ir(ppy)₃ (ppy = 2-phenylpyridine), which is greatly influenced by vibration of the complex. General formalism of the emission spectrum is derived using a thermal vibration correlation function formalism for the transition between two adiabatic electronic states in polyatomic molecules. Displacements and Duschinsky rotation of potential energy surfaces are included within the framework of a multidimensional harmonic oscillator model. This formalism gives a reliable description of the emission spectrum of Ir(ppy)₃. The calculated results indicated that the 0→1 transition between the T₁ state and the S₀ state makes a large contribution to the emission spectrum, especially the vibrational modes below 1600 cm^-1. The breathing vibration of the ligands and the CC and CN stretching vibrations of benzene and pyridine rings are the main reasons for the appearance of the shoulder peak in the spectrum. The Boltzmann distribution makes the intensities of both the main and the shoulder peaks decrease, and the peaks are close together. When coupled with first-principles density functional theory (DFT) calculations, the present approach appears to be an effective tool to obtain a quantitative description and detailed understanding of the spectra and photophysical processes of polyatomic molecules.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

位移谐振子模型对三(2-苯基吡啶)合铱磷光光谱影响的理论研究

English

Theoretical Study of the Phosphorescence Spectrum of Tris(2-phenylpyridine)iridium Using the Displaced Harmonic Oscillator Model

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

位移谐振子模型对三(2-苯基吡啶)合铱磷光光谱影响的理论研究

English

Theoretical Study of the Phosphorescence Spectrum of Tris(2-phenylpyridine)iridium Using the Displaced Harmonic Oscillator Model

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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