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研究生: 許雅筑
HSU,YA-CHU
論文名稱: 2,4–雙氟苯甲醚之第一電子激發態暨 離子態振動光譜
Vibronic and Cation Spectroscopy of 2,4-difluoroanisole
指導教授: 曾文碧
Tzeng, Wen-Bih
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: 130
中文關鍵詞: 共振雙光子游離光譜法質量解析臨界游離光譜法2,4–雙氟苯甲醚第一電子躍遷能游離能
英文關鍵詞: resonant two-photon ionization, mass-analyzed threshold ionization, 2,4–difluoroanisole, vibronic spectra, cation spectra
論文種類: 學術論文
相關次數: 點閱:224下載:3
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  • 我們應用高解析度共振雙光子游離(R2PI)與質量解析臨界游離光譜法(MATI),探討2,4–雙氟苯甲醚(2,4–difluoroanisole)的分子特性,精準地量測第一電子躍遷能與游離能,並記錄此分子的S1電子激發態和D0離子基態的振動光譜。D0離子基態光譜是利用第一電子激發態的00、X1、τCH3、151、9a1、6a1和11分子振動態為中間能階紀錄的。2,4–雙氟苯甲醚的第一電子躍遷能測得為35556 ± 2 cm-1,其游離能為67568 ± 5 cm-1。
    在光譜上所看到大部份的振動模式,都和芳香環上的平面運動有關。比較本實驗所得到的2,4–雙氟苯甲醚和文獻上苯甲醚的光譜數據
    ,可以幫助我們了解氟的取代基效應在苯甲醚上,對電子躍遷和游離過程及分子振動的影響。另外我們也利用ab initio及密度泛函數理論計算來幫助我們進行分子光譜標定工作。

    We applied the resonant two-photon ionization (R2PI) and mass-analyzed threshold ionization (MATI) spectroscopic techniques to record the vibronic and cation spectra of 2,4–difluoroanisole. The cation spectra were obtained by ionizing via the 00, X1, τCH3, 151, 9a1, 6a1, and 11 levels of the electronically excited S1 state. The band origin of the S1 ← S0 electronic transition of 2,4–difluoroanisole appears at 35556 ± 2 cm-1 and the adiabatic ionization energy is determined to be 67568 ± 5 cm-1.
    Most of the active vibrations of this molecule in the S1 and D0 states are related to in-plane vibrations of the aromatic ring. Comparing the experimental data of 2,4–difluoroanisole with those of anisole helps us learn the fluorine substitution affects on the electronic excitation and ionization processes as well as molecular vibration. We have also performed the ab initio and density functional calculations which help us in spectral assignment and support our experimental findings.

    中文摘要 I 英文摘要 II 目錄 III 圖目錄 V 表目錄 VII 一、 簡介 1 二、 研究目的 6 三、 光譜技術 9 1. 單色共振雙光子游離(one-color resonant two-photon ionization, 1C-R2PI)光譜術 9 2. 雙色共振雙光子游離(two-color resonant two-photon ionization, 2C-R2PI)光譜術 13 3. 質量解析臨界游離光譜術(MATI spectroscopy) 18 四、 實驗儀器 26 1. 真空系統 26 A. 束源氣室 30 B. 分子和雷射作用區 34 C. 飛行導管 36 D. 離子偵測區 37 2. 雷射系統 41 A. 固態銣釔鋁石榴石雷射(neodymium-doped yttrium aluminum garnet, Nd:YAG laser) 41 B. 染料雷射(Dye Laser) 45 3. 同步與訊號收集 50 五、 實驗過程 54 1. 實驗前準備 54 2. 實驗中 57 六、 理論計算與光譜分析 65 1. 概論 66 2. 基底函數 77 3. 光譜標定(spectral assignment) 81 七、 實驗結果 89 1. 2,4–雙氟苯甲醚之第一電子激發態振動光譜 89 2. 2,4–雙氟苯甲醚之PIE curve及MATI光譜對照圖 95 3. 2,4–雙氟苯甲醚之質量解析臨界游離光譜圖 98 4. 改變U1脈衝電場對於質量解析臨界游離光譜的影響 107 八、 結果討論 111 1. 躍遷能與游離能探討 111 2. 分子振動之探討 115 九、 結論 121 十、 參考文獻 123

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