林聖賢臺灣大學：化學研究所黃思維Huang, Ssu-WeiSsu-WeiHuang2007-11-262018-07-102007-11-262018-07-102006http://ntur.lib.ntu.edu.tw//handle/246246/51942在此篇論文中，我們利用共振雙光子游離術以及質量解析臨界游離術測量了鄰－二甲氧基苯激發態S1和離子態D0的振動光譜。得到S1←S0躍遷能量35750 ± 2 cm-1和絕熱游離能61617 ± 5 cm-1。並且我們也利用理論計算對振動光譜做合理的指派以及游離能的預測。最後將把結果與其他苯衍生物的結果相互比較，而進一步得到取代基效應和鄰近效應對電子躍遷、游離能及分子振動的影響。We use the resonant two-photon ionization (R2PI) and mass analyzed threshold ionization (MATI) spectroscopic techniques to record the vibrationally resolved spectra of o-dimethoxybenzene. The band origin of the S1←S0 electronic transition is found to be 35750 ± 2 cm-1 and the adiabatic ionization energy is 61617 ± 5 cm-1. By analying the ab initio and density functional calculations, we can give the spectral assignment to the spectrum and propose possible interpretation for our experimental finding. Finally, we compare o-dimethoxybenzene with other benzene derivatives to discuss the influence of vicinal substitution effect and substituent group effect on the electronic transition, ionization energy and molecule vibration.目錄 中文摘要………………………………………………………………..Ⅰ 英文摘要………………………………………………………………..Ⅱ 目錄……………………………………………………………………..Ⅲ 圖目錄…………………………………………………………………..Ⅴ 表目錄…………………………………………………………………..Ⅵ 一、簡介…………………………………………………………………..1 二、研究目的……………………………………………………………..3 三、實驗方法……………………………………………………………..5 1.共振多光子游離光譜術……………………………………………...5 2.質量解析臨界游離光譜術………………………………………….10 四、實驗儀器及設備……………………………………………………20 1.真空系統…………………………………………………………….20 2.雷射系統…………………………………………………………….26 3.同步及信號收集…………………………………………………….30 4.實驗過程…………………………………………………………….33 五、理論計算…………………………………………………………....37 1.概論………………………………………………………………….37 2.基底函數組………………………………………………………….44 3.鄰-二甲氧基苯分子的理論計算…………………………………....47 六、結果………………………………………………………………..57 1.單色雙光子光譜…………………………………………………….57 2.雙色雙光子光譜…………………………………………………….63 3.質量解析臨界游離光譜…………………………………………….65 七、討論………………………………………………………………..70 1.取代基效應對分子振動的影響…………………………………….70 2.鄰近效應對分子振動的影響……………………………………….73 3.影響游離能的因素………………………………………………….76 八、結論………………………………………………………………..79 九、參考文獻……………………………………………………….…..81 附錄一、O- di- “light” 的振動模式、標定及頻率範圍……………….87 附錄二、 鄰-二甲氧基苯分子的五種轉動運動………..……….881117898 bytesapplication/pdfen-US鄰-二甲氧基苯質量解析臨界游離光譜o-dimethoxybenzeneMass-analyzed threshold ionization spectroscopythesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/51942/1/ntu-95-R93223007-1.pdf