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研究生:梁記偉
研究生(外文):Chi-Wei Liang
論文名稱:雙光子雷射光譜對丙烯基-h5與丙烯基-d5之雷得堡電子態及游離能的相關研究
論文名稱(外文):Two-photon resonant ionization spectroscopy of the allyl-h5 and allyl-d5 radicals: Rydberg states and ionization energies
指導教授:陳逸聰陳逸聰引用關係
指導教授(外文):Yit-Tsong Chen
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
論文頁數:57
中文關鍵詞:丙烯基熱解游離能雷得堡電子態雙光子雷射光譜
外文關鍵詞:allyl radicalpyrolysisionizationRydberg stateREMPI
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使用雷射2+1 REMPI (Resonance Enhanced Multiphoton Ionization) 技術研究丙烯基-h5 (allyl-h5 radical,C3H5)和丙烯基-d5 (allyl-d5 radical,C3D5)在6.2-8.2 eV高電子態光譜。進行實驗所需要的自由基是將起始物C3H5I (或C3D5Br)由脈衝閥門以超音速噴出,經由位於脈衝閥門延伸端的熱解裝置斷鍵產生。結合本實驗室之前對丙烯基-h5的研究成果,我們綜合觀察到的光譜包括丙烯基-h5的ns (n=4-12)以及丙烯基-d5的ns (n=4-10)雷得堡電子態。在觀察丙烯基-h5和丙烯基-d5的電子振動光譜時,發現v7 ( ∠CCC對稱彎曲 )在兩個分子中都是最顯著的振動模式,其頻率分別為 ~440 cm-1以及 ~360 cm-1。藉由 ab initio方法計算出Franck-Condon factors (FCF),也幫助我們辨認出圖譜中的v5 (CH2 rocking)和v6 (C3 stretching)等兩種振動模式。將我們所觀察到的電子態能量代入Rydberg 公式可以得到丙烯基-h5和丙烯基-d5游離能的收斂值,分別是65594 ± 9 cm-1(8.133 ± 0.001 eV);和 65527 ± 16 cm-1 (8.1242 ± 0.002 eV)。

The Rydberg states of allyl-h5 and allyl-d5 radicals have been studied by using 2+1 REMPI method in the region of 6.2-8.2 eV. In this experiment flash pyrolysis was utilized to produce the allyl radicals. We observed newly reported ns Rydberg states of allyl-h5 radical, where n=4-12; and that of allyl-d5 for n=4-10. In these spetra, we found that the C3 symmetric bending mode, v7, is most dominant among the normal modes, and the frequencies of v7 in allyl-h5 and allyl-d5 are ~440 cm-1 and ~360 cm-1, respectively. By the help of ab inition calculation of Franck-Condon factors (FCF), we facilitated the procedure to assign the vibronic states we obtained. In addition to v7, we also identify v5 (CH2 rocking) and v6 (C3 stretching). By the regression procedure of Rydberg formula, we predicted the ionization energies of allyl-h5 and allyl-d5 radicals respectively are 65594 ± 9 cm-1(8.133 ± 0.001 eV) and 65527 ± 16 cm-1 (8.1242 ± 0.002 eV).

第一章 緒 論--------------------------------------- 1
第二章 實 驗
Ⅰ 儀器 --------------------------------------- 4
Ⅱ 實驗方法 --------------------------------------- 6
第三章 結果與討論
Ⅰ 實驗紀錄 --------------------------------------- 9
Ⅱ Franck-Condon factors -------------------------- 11
Ⅲ ns 雷得堡電子態 ------------------------------ 13
Ⅳ 丙烯基-h5和丙烯基-d5的游離能 ------------------ 19
第四章 結 論 ------------------------------------- 24
參考文獻 ----------------------------------------- 25
附錄 ---------------------------------------------- 29
表 ------------------------------------------------ 35
圖 ------------------------------------------------ 45

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