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研究生: 鄭旭翔
論文名稱: 利用飛秒瞬態吸收光譜技術研究不同溶劑中4-苯胺基反式雙苯乙烯與4-對苯腈基苯胺基反式雙苯乙烯 之激發態動力學
The Excited-State Dynamic of trans-4-(N-phenylamino)stilbene and trans-4-(N-(4-cyanophenyl)amino)stilbene Studied by Femtosecond Transient Absorption Spectroscopy
指導教授: 陳益佳
口試委員: 鄭博元
張智煒
陳益佳
學位類別: 碩士
Master
系所名稱: 理學院 - 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: 90
中文關鍵詞: 超快雷射瞬態吸收反式雙苯乙烯動力學模型
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  • 我們研究反式對位苯胺基雙苯乙烯(trans-4-(N-phenylamino)stilbene, p1H),以及反式對位對苯腈基苯胺基雙苯乙烯(trans-4-(N-(4-cyanophenyl)amino)stilbene, p1CN)之溶劑效應與其光激發態動力學模型。經由穩態吸收/螢光光譜之結果,推算出兩種化合物之激發態偶極矩,p1H之PICT能階為11.3 D,p1CN之PICT為9.3 D,而TICT為16.2 D。而由瞬態吸收光譜之數據可知,p1H與p1CN由330 nm激發到Franck-Condon能階後,會很快的產生電荷轉移變為PICT能階,時間常數約為0.7~1.8 ps,而PICT之緩解機制則在兩種化合物中有所不同,p1H之PICT只會經由放出螢光與光異構化回到基態,時間常數落在10~120 ps之間,隨著溶劑之黏度與極性而變,而p1CN則可經由轉為TICT緩解,TICT生成之時間常數約在5~30 ps之間,隨溶劑之黏度與極性而變,其能障高低隨溶劑之極性增加而降低,但也隨黏度增加而增高。而在不同溶劑下,TICT之生命期τ_3^TICT均比PICT之τ_3^PICT短約25%,表示TICT之電荷重組速率較快,因此推測在p1CN中,扭轉之分子結構可能會增進其電荷重組效率。而根據p1H及p1CN在EtOH中之表現差異來看,在p1CN中,氫鍵造成的效應非常明顯,但p1H則否,暗示了-CN取代基的存在會大幅增益氫鍵造成的內轉換效益。


    目錄 表目錄 iv 圖目錄 v 第1章 序論 1 1.1 前言 1 1.2 文獻回顧 2 1.2.1 反式雙苯乙烯(trans-stilbene) 2 1.2.2 推/拉電子系統(push-pull system) 4 1.2.3 反式-胺基雙苯乙烯(trans-aminostilbene) 10 第2章 系統儀器架設 17 2.1 穩態吸收以及螢光光譜儀 17 2.2 時間相關單一光子計數器(time-correlated single photon counting, TCSPC) 17 2.3 飛秒瞬態吸收光譜儀 20 2.3.1 超快雷射系統 21 2.3.2 調變雷射波長 24 2.3.3 瞬態吸收光譜儀 27 2.4 實驗條件 31 第3章 結果 33 3.1 簡介 33 3.2 p1H 35 3.2.1 穩態吸收與螢光光譜 35 3.2.2 螢光生命期偵測 36 3.2.3 瞬態吸收光譜 36 3.3 p1CN 37 3.3.1 穩態吸收與螢光光譜 37 3.3.2 螢光生命期偵測 38 3.3.3 瞬態吸收光譜 38 第4章 指認與討論 77 4.1 穩態吸收與螢光光譜 77 4.2 時間解析光譜 78 4.2.1 p1H之能量釋解機制探討 78 4.2.2 p1CN之能量釋解機制探討 79 第5章 結論與展望 86

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