臺灣博碩士論文加值系統

本論文利用自行架設之克爾光閘時間解析螢光光譜儀(optical kerr gating time-resolved fluorescence spectroscopy)探討甲基取代苯(p-XY,TOL,BZ)與四氰基乙烯(TCNE)在CCl4和CH2Cl2溶劑中形成的電子給體-受體錯合物，以飛秒雷射脈衝激發甲基取代苯-四氰基乙烯錯合物的電荷轉移吸收譜帶(charge transfer band)，再搭配時間解析螢光光譜 (time-resolved fluorescence, TRFL)與理論計算結果探討三種錯合物從激發態回到基態的動態學過程。我們提出一個總發光強度函數P(t)用來描述激發態分子在鬆弛(relaxation)過程中，激發態佈居數(population)與躍遷偶極矩(transition dipole moment)隨時間的變化，我們可以觀察到三種錯合物在CH2Cl2和CCl4溶劑中都存在一個非常快的衰減成分(< 0.2 ps)，我們將此過程指認為CT2→CT1的IC。在極性溶劑CH2Cl2中，p-XY-TCNE( 、415 nm)、TOL-TCNE( nm)和BZ-TCNE( nm)的電荷再結合時間常數分別為0.6 ps、0.5 ps、7 ps及29 ps。在非極性溶劑CCl4中，p-XY-TCNE( 、415 nm)、TOL-TCNE( nm)和BZ-TCNE( nm)的電荷再結合時間常數分別為280 ps、280 ps、850 ps及150 ps。 我們觀察到甲基取代苯-四氰基乙烯在CH2Cl2溶劑中的電荷再結合速率非常符合Marcus反轉區域(inverted region)，即驅動力(driving force, )愈大會使得電子轉移速率愈慢；然而在CCl4溶劑中， BZ-TCNE錯合物卻明顯偏離Marcus反轉區域，我們利用交叉態模型(intersecting state model, ISM)解釋其偏差，即必須考慮錯合物結構改變的影響，ISM提出Marcus理論中兩條位能曲面不只會垂直移動也會水平移動，使得反應能障 發生變化進而影響電子轉移速率。最後，我們比較在不同極性溶劑中對錯合物電荷再結合速率的影響，可以觀察到極性溶劑中的電荷再結合速率明顯較快，這是因為強大的polar solvation效應所造成。值得注意的是，p-XY-TCNE和TOL-TCNE錯合物在CH2Cl2溶劑中的電荷再結合皆應發生在未平衡狀態，即尚未完全solvation或振動鬆弛就回到基態。

We employed a broadband ultrafast time-resolved fluorescence (TRFL) spectrometer implemented by the optical Kerr gating (OKG) to study the charge transfer (CT) state dynamics of methyl-substituted benzene-tetracyanoethylene (MBZ-TCNE, MBZ = benzene, toluene and p-xylene) in two solvents (CH2Cl2, CCl4) of diffrernt polarities. The CT-state of the MBZ-TCNE complexes are reached via femtosecond laser excitation, and the observed TRFL spectra reveal CT-state relaxation dynamics from the initial CT-state to charge recombination (CR). We used a total fluorescence intensity function P(t) to describe the excited-state population and transition dipole moment evolution with time during CT-state relaxation. The three complexes studied in two solvents exhibit a very fast initial decay component of similar time scale (< 0.2 ps), which can be assigned to CT2→CT1 internal conversion. The CR time constants for p-XY-TCNE (λex = 383 nm), TOL-TCNE ( nm) and BZ-TCNE ( nm) are 0.6, 7 and 29 ps in CH2Cl2. The equilibrium CR time constants for p-XY-TCNE
(λex = 383 nm), TOL-TCNE ( nm) and BZ-TCNE ( nm) are 280, 850 and 150 ps in CCl4. The CR rate constants of MBZ-TCNE in CH2Cl2 are in line with the expectation for the Marcus inverted region, but CR rates in CCl4 do not agree with Marcus inverted region. The unexpected reversed -G0 dependence of the equibrium CR rates in CCl4 can be explained by the intersecting state model (ISM), which takes structural relaxation of complexes into account. Finally, CR rates of the CT-state of these MBZ-TCNE complexes are much faster in polar solvents due to the strong polar solvation.

摘要 i
Abstract ii
謝誌 iii
目錄 iv
第1章 緒論 1
1.1 電子轉移前言 1
1.2 電子轉移理論 3
1.3 EDA Complex簡介 11
1.4 本論文研究目的 24
第2章 實驗系統與技術 26
2.1 超快飛秒雷射系統 26
2.1.1 雷射產生源 27
2.1.2 能量放大器 30
2.2 實驗技術 34
2.2.1 Optical Kerr Gating簡介 34
2.2.2 時間解析克爾光閘螢光光譜實驗系統與組成 35
2.2.3 超快時間解析克爾光閘螢光光譜實驗自動化數據擷取系統 46
2.3 時間解析克爾光閘螢光光譜儀的校正 49
2.3.1 光譜靈敏度的校正 49
2.3.2 時間延遲(temporal delay)校正 55
2.4 時間解析克爾光閘螢光光譜儀正確性探討 59
2.5 EDA Complexes溶液的製備 60
2.5.1 TCNE的空白實驗 62
第3章 結果與討論 64
3.1 p-XY-TCNE、TOL-TCNE和BZ-TCNE錯合物於CH2Cl2、CCl4溶劑中的靜態光譜 64
3.2 p-XY-TCNE、TOL-TCNE和BZ-TCNE於CH2Cl2、CCl4溶劑中的時間解析螢光光譜 74
3.2.1 p-XY-TCNE於CH2Cl2溶劑中的時間解析螢光光譜 76
3.2.2 p-XY-TCNE於CCl4溶劑中的時間解析螢光光譜 91
3.3 p-XY-TCNE基態與激發態之理論計算結果 104
3.3.1 基態結構與能量 104
3.3.2 垂直激發能量計算結果 111
3.3.3 CT態結構與能量 119
3.4 綜合討論 125
3.4.1 時間解析動態螢光Stokes shift與螢光放光平均頻率 125
3.4.2 總螢光衰減函數 128
3.4.3 螢光衰減動態學模型 132
3.5 結論 136
參考文獻 138

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