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研究生： 李垠輯
Li, Yin-Ji
論文名稱： 氘化鈉分子第一單重激發態與部分基態之雷射光譜探討
Laser Spectroscopic Study of the NaD First Excited Singlet State and Parts of the Ground 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： 2013
畢業學年度： 101
語文別： 中文
論文頁數： 167
中文關鍵詞： 雷射光譜 、氘化鈉 、激發光譜 、雙光子共振 、分子常數 、RKR位能曲線
外文關鍵詞： Laser spectroscopy, NaD, Excitation spectroscopy, Optical-optical double resonance, Molecular constant, RKR potential curve
相關次數： 點閱：129  下載：1 
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    • 在本論文中，利用掺銣石榴石雷射激發染料雷射產生可調波長的雷射光來激發氘化鈉分子的光譜來探討氘化鈉分子的基態(X1Σ+能態)與第一單重激發態(A1Σ+能態)。
    論文的第一部分是利用激發光譜法收集氘化鈉分子由X1Σ+能態(v”=0, J”)激發至A1Σ+能態(v’, J’)後的自發放射產生的螢光訊號來了解A1Σ+能態的特性。實驗上一共使用四種染料：LDS 759(以二倍頻系統激發)、Exalite 392E、Exalite 400E、Stilbene 420、Coumarin 440(以三倍頻系統激發)產生雷射波長370~434 nm。共收集730條躍遷訊號，振轉能級範圍為v’=5~19, J’=0~24。在量子數確認的部份是利用雷射誘導螢光光譜法來確認收集到的訊號的確切振轉能級。根據實驗觀測到的訊號，經由擬合得到氘化鈉分子A1Σ+能態每一個振動態的振動能級能量(Gv)、轉動常數(Bv)及離心形變常數(Dv)。由實驗結果可推導出一組登亥姆分子常數與RKR位能曲線，此結果比文獻所報導的值更準確。
    論文的第二部分是利用雙光子共振螢光減量光譜法收集氘化鈉分子由A1Σ+能態(v’, J’)誘導放射回到X1Σ+能態(v”=14、15, J”)所產生的螢光減量訊號可以探測基態X1Σ+的結構。實驗上使用染料DCM產生並收集雷射波長621~626 nm(v”=14)與643~649 nm(v”=15)共28條振轉能級躍遷訊號，觀測到的振轉能級範圍為v”=14、15, J”=3~11。根據雙光子共振螢光減量光譜所得到的螢光減量訊號，經過計算後得到氘化鈉分子X1Σ+能態v”=14與15的振動能級能量差(ΔGv+1/2)、轉動常數(Bv)並與文獻做比較。

    In this study, we investigated the fluorescence spectrum to explore the first excited singlet state A1Σ+ and the ground state X1Σ+ of NaD by laser excitation and laser induced fluorescence.
    In the first part, the fluorescence spectra produced by stimulated absorption from ground state X1Σ+ to the first excited A1Σ+ state of NaD molecule were recorded. Five different dyes: LDS 759 (pumped by the second harmonic 532 of Nd:YAG laser), Exalite 392E, Exalite 400E, Stilbene 420, and Coumarin 440 (pumped by the third harmonic 355 of Nd:YAG laser), were used to produce laser wavelength in the range from 370 to 434 nm. A total of 688 transitions were collected and assigned to the rovibrational quantum numbers of v’=5~19, J’=0~24. The quantum number assignment was confirmed by laser-induced fluorescence spectroscopy. According to the signals recorded in the experiment, the vibrational terms (Gv), the rotational constant (Bv), and the centrifugal distortion constant (Dv) were determined for each rovibrational level. A set of Dunham coefficients, and RKR potential curve for A1Σ+ state of NaD are generated and the accuracy is improved compared to the previous literature reports.
    In the second part, the laser induced emission signals of NaD molecule relaxed from the intermediate state (A1Σ+(v’,J’)) to ground state (X1Σ+(v”=14-15, J”)) by optical-optical double resonance fluorescence depletion spectroscopy were recorded. The spectra were taken in the laser wavelength of (621~626 nm (v”=14) and 643~649 nm (v”=15)) which were produced by DCM dye. A total of 28 rovibrational transitions were collected and assigned to the rovibrational levels v”=14 and 15, J”=3~11. According to the signals detected in the experiment, the vibrational term (Gv), and the rotational constant (Bv) of vibrational levels v”=14 and 15 were determined in the X1Σ+ state of NaD.

    中文摘要 I 英文摘要 II 誌謝 III 目錄 IV 表目錄 VII 圖目錄 XI 第一章 緒論 1 1.1 研究動機與背景 1 1.2 文獻回顧 5 1.2.1 氘化鈉 5 1.2.2 氫化鈉 8 第二章 量子理論 12 2.1 雙原子分子的能量 12 2.1.1 薛丁格方程式 12 2.1.2 波恩-奧本海默近似法 13 2.1.3 登亥姆展開式 15 2.1.4 登亥姆係數 16 2.1.5 RKR位能曲線 18 2.2 分子光譜 20 2.2.1 項符 20 2.2.2 選擇律 22 2.2.3 法蘭克-康登原理 23 2.3 同位素位移 24 第三章 實驗 27 3.1 實驗裝置 27 3.1.1 雷射系統 27 3.1.2 熱管爐系統 29 3.1.3 訊號偵測系統 30 3.1.4 訊號收集系統 31 3.1.5 雷射波長校正系統 33 3.2 實驗藥品 34 3.3 實驗原理 35 3.3.1 A1Σ+能態 35 3.3.2 X1Σ+能態或其他更高能態 38 第四章 氘化鈉分子A1Σ+能態的研究 41 4.1 訊號的確認與校正 42 4.1.1 Dye LDS 759 42 4.1.2 Dye Exalite 392E 44 4.1.3 Dye Exalite 400E 46 4.1.4 Dye Exalite 400E Combined Stilbene 420 49 4.1.5 Dye Stilbene 420 52 4.1.6 Total Peaks 55 4.1.7 Laser Induced Fluorescence 58 4.2 氘化鈉分子A1Σ+能態的分子常數 60 4.3 氘化鈉分子登亥姆係數與RKR曲線 67 4.4 結論 70 第五章 氘化鈉分子X1Σ+能態的研究 71 5.1 訊號的確認與校正 72 5.2 氘化鈉分子X1Σ+能態的分子常數 76 5.3 結論 79 參考文獻 80 附錄 83 附錄A 中空陰極管校正譜線 84 附錄B 激發光譜圖 93 附錄C 由基態振動能級v’=0激發至第一單重態的訊號 113 附錄D 由基態振動能級v’=1激發至第一單重態的訊號 121 附錄E 第一單重態不同振動能級的分子常數計算結果 124 附錄F 所有躍遷計算登亥姆係數結果 154 附錄G基態與第一單重態間的法蘭克-康登因子表 163 附錄H 雙光子共振螢光減量光譜雷射能量與能態總表 165 附錄I 基態不同振動能級的分子常數計算結果 166

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