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研究生：	姜宗螢 Tzung-Ying Jiang
論文名稱：	以理論計算探討重原子過渡金屬其激發態動力學分析和放光性質 A Theoretical Investigation on Excited State Dynamics and Luminescent Properties of Heavy Transition metal complexes
指導教授：	李祐慈 Li, Yu-Tzu
學位類別：	碩士 Master
系所名稱：	化學系 Department of Chemistry
論文出版年：	2014
畢業學年度：	102
語文別：	中文
論文頁數：	131
中文關鍵詞：	有機發光二極體、過度金屬錯合物、重原子效應、自旋-軌道耦合作用力、系統間跨越、磷光
英文關鍵詞：	Organic light-emitting diode, transition metal complexes, heavy atom effect, spin-orbit coupling, Intersystem crossing, phosphorescence
論文種類：	學術論文
相關次數：	點閱：142 下載：22
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本論文將探討過渡金屬錯合物之光物理性質，特別針對過渡金屬錯合物Sn 到Tm之間系統間跨越（Intersystem crossing, ISC）的速率之影響參數進行研究。過渡金屬錯合物中心的重原子效應產生之強自旋-軌道交互作用力（spin-orbit coupling, SOC），可以增強系統間跨越的效率，使其有利於放出磷光。若能有效的提升系統間跨越的效率，就可間接加強過渡金屬錯合物放光的量子產率，因此ISC速率的大小是很多光電材料應用上的關鍵因素。本篇將對各種不同類別的發光過渡金屬錯合物進行討論，以理論計算方法預測這些過渡金屬的光物理性質，並與實驗數據相互比較。最終希望能找出影響過渡金屬化合物自旋-軌道耦合（spin-orbit coupling）作用力大小和ISC量子產率之定量關係式的各種因素，如電子結構，如原子序、鍵長、電子躍遷性質、單重態與三重態能階差等。
　　我們主要以鋨(Osmium) 、釕(Ruthenium)和銅(Copper)、銀(Silver)、金(Gold)等過渡金屬錯合物為討論對象，探討metal-to-ligand charge transfer（MLCT）和中心金屬d軌域對自旋-軌道耦合之影響，以定量的方式計算出自旋-軌道耦合強度大小，並比較內部重原子效應(Internal heavy atom effect)和外部重原子效應(External heavy atom effect)對系統間跨越的差異性。而在最後一部分探討鋨(Osmium)系列過渡金屬錯合物在較高激發態(High-lying excited state)系統間跨越的反應速率遠高於S1→Tm的系統間跨越反應速率之特殊性質。
關鍵字:有機發光二極體,過度金屬錯合物,重原子效應,自旋-軌道耦合作用力,系統間跨越,磷光

In this thesis, we provide a systematic elucidation on the parameters that influence the Sn to Tm intersystem crossing rate (ISC) constant of emissive transition metal complexes, which is a crucial factor in many optoelectronic device applications. Particular attention will be paid to the derivation of rate constant of Sn  Tm ISC based on a non-adiabatic approach. Extensive theoretical calculations on a large set of different families of known emissive TM complexes, and a careful comparison between and theoretical predictions and experimental behaviors are performed. The ultimate goal in this thesis is to summarize practical and quantitative rules that govern the magnitude of spin-orbit coupling (SOC) integrals and the overall ISC quantum yield, including the atomic number, bonding distance, types of transition, electronic energy gaps, vibrational relaxations, and etc.
Systems mainly studied in this thesis include osmium, ruthenium and copper, silver, gold transition metal complexes. We first explore quantitatively how the metal-to-ligand charge transfer (MLCT) property and the percentage of the central metal d orbital involvement Influence the intersystem crossing rate by quantitatively computing the SOC integrals. In the second part, we compare the internal heavy atom effect and external heavy atom effect for the Group 11 d10 Cu(I), Ag(I), and Au(I) transition metal complexes. Finally, we investigate the spin-orbit coupling strength between the high-lying excited states and lowest-lying excited state for a class of Os(II) complexes.
關鍵字:Organic light-emitting diode,transition metal complexes,heavy atom effect,spin-orbit coupling,Intersystem crossing,phosphorescence

目錄 I
圖目錄 IV
表目錄 VII
摘要 IX
Abstract X
第一章　緒論 1
1-1有機發光二極體發光原理 1
1-2發光二極體結構 1
1-3三重態獲益(Triplet harvesting)2
1-4單重態獲益(Singlet harvesting)3
1-5主體與客體間的電子轉移 5
1-6研究目標 6
第二章　計算原理和方法 7
2-1計算化學原理 7
2-2密度泛函理論(Density Functional Theory) 9
2-3基底函數(Basis Set) 10
2-3-1極化函數(Polarization Function) 12
2-3-2擴散函數(Diffuse Function) 13
2-3-3有效核位能(Effective Core Potential) 13
2-4微擾理論(Perturbation theory) 14
2-5相對論效應(Relativistic effect)14
2-6 光物理反應參數    16
2-6-1量子產率 16
2-6-2幅射衰變速率常數之推導（Formalism for the Radiative Decay Rate constant）17
2-7自旋-軌道耦合交互作用 18
2-8本篇使用之計算方法 22
2-8-1單點能量(Single point) 22
2-8-2幾何優化(Geometry optimization) 23
2-8-3溶劑模型(Solvation Model) 23
2-8-4本篇採用的計算方法參數 25
第三章　鋨過渡金屬錯合物之激發態電子結構對系統間跨越影響之定量分析    26
Quantitative analysis of MLCT contributions to ISC rates in β-diketonate　Os(II) complexes    26
3-1系統介紹    26
3-2鋨過渡金屬錯合物之激發態電子結構 28
3-3自旋軌域耦合強度的初步估計 32
3-4自旋軌域耦合強度的進階計算與討論 41
3-4-1 比較一級與二級微擾理論推導之磷光衰變常數    41
3-4-2 單重態至三重態之自旋軌域耦合積分值與主要系統間跨越路徑 42
3-4-3 激發態電子結構與自旋軌域耦合積分值的定量關係 44
3-4-4 計算結果與實驗觀察之對應 45
3-5結論    48
第四章　亞銅、銀與金一價錯合物之重金屬效應探討Internal v.s external heavy atom effects in Cu(I),Ag(I), Au(I) complexes 50
4-1系統介紹 50
4-2亞銅、銀與金一價錯合物之激發態電子結構 52
4-3自旋軌域耦合強度的初步估計 55
4-4自旋軌域耦合強度的進階計算與討論 60
4-5結論    68
第五章 鋨過渡金屬錯合物之高激發態間系統間跨越性質研究 69
High-lying state ISC rates in Os(II) complexes    69
5-1系統介紹 69
5-2 計算結果 71
5-3 結論    75
總結論 76
參考文獻 78
附件一 附圖和附表 81
附件二 期刊論文草稿    103
                                

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