本論文利用實驗室自行架設的飛秒瞬態吸收光譜儀(transient absorption, TA)及一套自動化數據擷取電腦程式，研究電子給體-受體(electron donor-acceptor, EDA)錯合物的分子間電荷轉移動力學行為。研究對象為苯/四氰基乙烯(benzene/tetracyanoethylene, BZ/TCNE)錯合物溶於不同比例之苯/二氯甲烷及苯/乙腈混合溶劑。本論文分為三個主題：第一個是觀察直接激發BZ/TCNE錯合物於二氯甲烷溶劑中的電荷轉移(charge transfer, CT)態後的電荷轉移動力學；第二個是觀察直接激發BZ/TCNE錯合物於乙腈溶劑中的CT態後的電荷轉移動力學；第三個是研究激發於苯/二氯甲烷混合溶劑中的電子受體TCNE，使TCNE激發至其S1態或BZ/TCNE錯合物被激發至LE態，並且觀察其後續電荷轉移的動力學過程。
在第一及第二個主題中，我們觀察到四氰基乙烯自由基陰離子(TCNE-)與苯二聚體自由基陽離子((BZ)2+)的光譜特徵及其時間變化之行為，並與過去本實驗室激發BZ/TCNE錯合物於四氯化碳溶劑中的CT態後的電荷轉移動力學進行比較。我們觀察到激發錯合物CT態後，激發態錯合物會先進行較快的溶劑及振動緩解，接著為較慢的電荷再結合(charge recombination, CR)反應。其中電荷再結合過程之時間常數，於乙腈溶劑中最短，於二氯甲烷溶劑中次之，於四氯化碳溶劑中最長。
在第三個主題中，我們藉由第一個主題得到的光譜幫助指認BZ/TCNE錯合物的CT態光譜，並根據本實驗室前人提出的動力學模型來描述激發TCNE至其S1態或BZ/TCNE錯合物被激發至其電子給體LE態，經由電荷轉移生成BZ/TCNE的CT態錯合物以及其後續衰減動力學。我們觀察到BZ/TCNE錯合物於二氯甲烷溶劑中由其LE態進行電荷轉移至CT態之時間常數約為0.3 ps，我們發現此時間常數比實驗室前人過去研究BZ/TCNE錯合物於四氯化碳中由其LE態進行電荷轉移至CT態之時間常數(約0.2 ps)相比之下來的稍慢。

We study the charge-transfer (CT) dynamics of the electron donor-acceptor (EDA) complexes with broadband femtosecond transient absorption (TA) spectroscopy. The EDA complex studied here are binary (1:1) and ternary (2:1) benzene/tetracyanoethylene (BZ/TCNE) dissolved in a series of benzene/dichloromethane and benzene/acetonitrile cosolvents. The thesis is mainly divided into three topics. In the first topic, we directly excite the CT state of BZ/TCNE complexes in dichloromethane. In the second topic, we directly excite the CT state of BZ/TCNE complexes in acetonitrile. In the third topic, we study the charge transfer kinetics after exciting TCNE to its S1 state in benzene/dichloromethane cosolvents or to the TCNE locally excited (LE) state of the BZ/TCNE complexes.
In the first and the second topics, we directly excite the CT states of BZ/TCNE complexes in dichloromethane and acetonitrile to observe their relaxation dynamics and compare the results with the previously-studied BZ/TCNE complexes in carbon tetrachloride. We observe spectral characteristics of tetracyanoethylene radical anion (TCNE-) and benzene dimer radical cation ((BZ)2+). By analyzing their time-dependent behaviors, we found that after exciting the CT state of BZ/TCNE complexes, the excited state complexes undergo rapid solvation and vibrational relaxation, followed by a slower charge recombination (CR) reaction. By comparing the CR process of BZ/TCNE complexes in carbon tetrachloride, we found that the CR time constants is fastest in acetonitrile, followed by that in dichloromethane, and the CR time constants is slowest in carbon tetrachloride.In the third topic, we study the charge transfer kinetics after exciting TCNE to its S1 state in benzene/dichloromethane cosolvents or to the TCNE locally excited (LE) state of the BZ/TCNE complexes. We identify the CT state spectra of BZ/TCNE complexes by comparing with those obtained from the first topic. An approximate kinetic model is proposed to describe the charge transfer that generates BZ/TCNE CT state complexes after excitation of TCNE S1 state in benzene/dichloromethane cosolvents or to the TCNE LE state of the BZ/TCNE complexes, and its subsequent relaxation kinetics. We observed that the LE→CT states charge transfer time constants in the BZ/TCNE complexes in dichloromethane are about 0.3 ps, which is slower than that (~0.2 ps) observed in previous studies in carbon tetrachloride.

摘要 ii
Abstract iii
謝誌 v
目錄 vii
圖目錄 x
表目錄 xv

第一章 序論 1
1.1 電荷轉移概論 1
1.2 電子轉移理論 3
1.3 EDA錯合物簡介 6
1.4 苯/四氰基乙烯錯合物電荷轉移動力學回顧 6
1.5 論文研究目的 9

第二章 實驗系統與技術 11
2.1超快飛秒雷射系統 11
2.1.1 飛秒雷射產生源 12
2.1.2 能量再生放大器 17
2.2 實驗技術 22
2.2.1 瞬態吸收光譜原理 22
2.2.2 瞬態吸收光譜系統之光路架設 25
2.2.2.1 以390 nm飛秒脈衝為激發光源之瞬態吸收光譜系統架設 25
2.2.2.2 以276 nm飛秒脈衝為激發光源之瞬態吸收光譜系統架設 27
2.2.3 瞬態吸收光譜自動化數據擷取系統 28
2.2.4 儀器響應函數 30
2.2.5 瞬態吸收光譜時間延遲校正 32
2.2.6 瞬態吸收光譜背景扣除 34
2.3 實驗藥品與EDA錯合物配置 38
第三章 以飛秒瞬態吸收光譜研究苯/四氰基乙烯錯合物於二氯甲烷中電荷轉移態緩解動力學 39
3.1 CT態靜態吸收光譜 39
3.2 以390 nm激發電荷轉移態之瞬態吸收光譜 43
3.2.1 各比例混合溶劑中以390 nm激發之瞬態吸收光譜 43
3.2.2 450±2 nm光區瞬態吸收動力學行為研究 53
3.2.3 850±12 nm光區瞬態吸收動力學行為研究 56
3.3綜合討論 60
3.3.1 BZ/TCNE錯合物CT態於二氯甲烷的緩解動力學討論 60
3.3.2 BZ/TCNE錯合物CT態於二氯甲烷與四氯化碳的緩解動力學比較 61
3.3.3不同類型CT態間轉移動力學討論 64

第四章 以飛秒瞬態吸收光譜研究苯/四氰基乙烯錯合物於乙腈中電荷轉移態緩解動力學 66
4.1 CT態靜態吸收光譜 66
4.2 以390 nm激發電荷轉移態之瞬態吸收光譜 68
4.2.1 各比例混合溶劑中以390 nm激發之瞬態吸收光譜 68
4.2.2 450±2 nm光區瞬態吸收動力學行為研究 74
4.2.3 850±12 nm光區瞬態吸收動力學行為研究 77
4.3綜合討論 80
4.3.1 BZ/TCNE錯合物CT態於乙腈的緩解動力學討論 80
4.3.2不同類型CT態間轉移動力學討論 82
第五章 以飛秒瞬態吸收光譜研究苯/四氰基乙烯錯合物於二氯甲烷中局部激發態電荷轉移動力學 84
5.1 BZ及TCNE單體之靜態吸收光譜 84
5.2 TCNE激發態電荷轉移動力學模型 85
5.3 276 nm激發瞬態吸收空白背景訊號扣除 87

5.4以276 nm激發之瞬態吸收光譜 91
5.4.1 各比例混合溶劑以276 nm激發之瞬態吸收光譜 91
5.4.2 450±2 nm光區瞬態吸收動力學行為研究 103
5.4.3 850±12 nm光區瞬態吸收動力學行為研究 106
5.5綜合討論 110
5.5.1 局部激發態於二氯甲烷的電荷轉移動力學討論 110
5.5.2 局部激發態於二氯甲烷與四氯化碳的電荷轉移動力學比較 112

第六章 結論 114

附錄 116
附錄一 390 nm激發動力學模型擬合過程 116
附錄二 276 nm激發動力學模型擬合過程 117

Reference 119

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