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研究生： 黃柏霖
Huang, Bo-Lin
論文名稱： 氣態氘化鈉分子21Π電子能態的光譜研究
Spectroscopic Study of the NaD 21Π State
指導教授： 黃守仁
Whang, Thou-Jen
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： 2016
畢業學年度： 104
語文別： 中文
論文頁數： 98
中文關鍵詞： 氘化鈉分子 、21Π能態 、雙光子共振螢光減量光譜法
外文關鍵詞： Sodium deuteride, 21Π state, Optical-optical double resonanc
相關次數： 點閱：161  下載：2 
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    • 本論文使用固態雷射Nd-YAG當作激發光源，將雷射導入兩套染料雷射系統，共用到三種光譜法，分別為激發光譜、雷射誘導光譜與雙光子共振螢光減量光譜，一步步確認實驗的狀態與條件，其中利用疊加式雙光子共振螢光減量光譜來研究氘化鈉分子的21Π電子能態，設計出電子的躍遷模式：
    X1S+(v"1,J"1) → A1S+(v',J')＋hυ1 (pump)(選擇率J'＝J"±1)
    A1S+(v',J') → 21Π(v,J)＋hυ2 (probe) (選擇率J＝J',J'±1)
    A1S+(v',J') → X1S+(v"2,J"2)＋hυ3 (fluorescence)
    實驗中選擇氘化鈉中間態A1S+的振動能階v’=15、16，且利用不同中間態來比對光譜的振轉能階訊號，現階段分析出21Π電子能態v*(J=1~6)、v*-1(J=1~8)、v*-2(J=1~10)等共24個振轉能階，轉動常數Bv值介在0.296~0.569 cm-1，振動能階能量差ΔGv+1/2為21.54與45.67 cm-1。
    由於目前並沒有關於氘化鈉21Π電子能態的文獻，可從幾篇氫化鈉21Π電子能態的文獻著手，利用同位素位移法與本實驗的數據相互探討。本論文擬合出一套氘化鈉21Π電子能態的分子常數，求得谷底值Te=44335.05 cm-1，ωe=248.14 cm-1，Be=1.57 cm-1，並修正RKR結果，獲得氘化鈉21Π電子能態的位能曲線，最後利用法蘭克-康登因子來確認絕對振動量子數。

    The purpose of the study was to observe the 21Π state of the NaD. The second and third harmonic of Nd-YAG served as the pumping source to pump first and second dye laser. By means of three kinds of spectra, included excitation spectroscopy, laser-induced fluorescence spectroscopy (LIF), and especially for Stepwise type optical-optical double resonance (OODR). The design of electronic transitions for the 21Π state of the NaD were summarized below：
    X1S+(v"1,J"1) → A1S+(v',J')＋hυ1 (pump)(selection rule J'＝J"±1)
    A1S+(v',J') → 21Π(v,J)＋hυ2 (probe)(selection rule J＝J' ,J'±1)
    A1S+(v',J') → X1S+(v"2,J"2)＋hυ3 (fluorescence)
    We used different the vibrational energy level of A1Σ+ state to obtain 24 rovibrational levels of 21Π state, v*(J=1~6)、v*-1(J=1~8) and v*-2(J=1~10). The study findings revealed a set of Dunhum coefficient via isotope shift in comparison to experimental data. In this work, we got Te=44335.05 cm-1, ωe=248.14 cm-1, Be=1.57 cm-1, and the modified potential energy curve of NaD 21Π state.

    表目錄 X 圖目錄 XI 第一章 緒論 1 1-1 前言與研究動機 1 1-2 氘化鈉分子的研究進程 6 1-3 氫化鈉分子21Π能態之文獻回顧 9 第二章 理論 13 2-1 雙原子分子的波函數 13 2-2 分子常數推導 14 2-3 雙原子分子的電子項符 17 2-4 罕德耦合(Hund’s coupling cases) 18 2-5 耦合分離(Uncoupling phenomenon) 19 2-6 選擇率(Selection rule) 20 2-7 分子躍遷強度 21 2-8 Rydberg-Klein-Ress(RKR)位能曲線 24 2-9 同位素位移 (Isotope shift) 25 第三章 實驗 28 3-1 實驗儀器裝置 28 3-1-1 雷射系統 28 3-1-2 熱管爐(Heatpipe oven), 30 3-1-3 偵測訊號系統 31 3-1-4 校正雷射波長 33 3-2 實驗藥品及染料 35 3-2-1 藥品 35 3-2-2 染料 35 3-3 實驗用的光譜法 37 3-3-1 激發光譜法(Excitation spectroscopy) 37 3-3-2 雷射誘導螢光光譜法(LIF) 38 3-3-3 雙光子共振螢光減量光譜法(OODR) 40 3-4 操作實驗達最佳化(實驗技巧) 44 3-4-1 雷射品質 44 3-4-2 光路調整 44 3-4-3 解決螢光微弱的方法 45 第四章 結果與討論 46 4-1 四、待完成實驗雷射波長校正 46 4-1-1 第一道染料雷射的校正 47 4-1-2 第二道染料雷射的校正 48 4-2 確認氣態氘化鈉的存在 49 4-3 氣態氘化鈉分子21Π能態的偵測 50 4-3-1 實驗結果 50 4-3-2 21Π能態訊號確認 53 4-3-3 21Π數據分析 57 4-3-4 Dunham 分子常數 58 4-3-5 振動常數Gv與轉動常數Bv 61 4-3-6 RKR位能曲線 63 4-3-7 法蘭克-康登因子(Franck-condon factor簡稱FCF) 68 4-3-8 氘化鈉21Π其它範圍的觀測 71 4-3-9 Λ簡併態的e/f parity對振轉能階的影響 74 4-4 待完成工作 75 第五章 結論 83 參考文獻 84 附錄 氘化鈉分子D1Σ+能態的研究成果 87

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