亞硝酸根(NO2-)水溶液是環境中OH與NO自由基的光解前驅物之一。由於近年來生物燃料逐漸取代部分化石燃料，大氣中CH3OH與C2H5OH的濃度隨著提升。然而NO自由基與醇類之反應動力學及NO2-水溶液於醇類存在下之光解反應動力學卻仍未被詳細探討。因此吾人將使用步進式時間解析紅外光譜儀觀測NaNO2水溶液與分別添加不同濃度CH3OH或C2H5OH的NaNO2水溶液受355 nm脈衝雷射激發後之時間解析紅外差異吸收光譜，並利用B3LYP密度泛函方法搭配基底函數aug-cc-pVTZ結合水溶劑效應(CPCM)，預測相關分子之絕對能量與簡諧振動波數等特性。NO2-水溶液受光解後，紅外光譜中於1 ms內1860-2030 cm-1之差異吸收度為正值，吾人將其指認為N2O3異構物為主的生成，此可能係因NO2-之光解產物NO自由基與NO2進行締合反應後所形成，其中NO2的來源為光解產物OH自由基與NO2-快速反應。當添加高濃度醇類後，N2O3之消逝反應速率些微變慢，依據反應機構與預測之反應熱，吾人認為是因N2O3與醇類之反應活性較與水之反應活性低，且加入高濃度醇類後使得溶液中水濃度下降所致。若比較N2O3於未添加及添加不同濃度CH3OH或C2H5OH中之消逝反應速率，吾人推算醇類與NO或NO2於水溶液中之反應速率常數上界約為7.3 × 103 M-1 s-1。此研究提供之醇類與NO、NO2及N2O3於水溶液中之反應光譜與動力學資訊，能夠協助更加了解醇類與NxOy物種於水溶液中與溼氣溶膠中之光化學反應機制。

Nitrite (NO2-) is regarded as a potential OH and NO precursor in aqueous solution upon ultraviolet photolysis. Besides, due to the usage of biofuels in recent years, the concentrations of CH3OH and C2H5OH have increased in the troposphere. However, the reaction kinetics of NO with alcohols and NO2- in alcohol-containing aqueous solutions after ultraviolet photolysis are insufficiently understood. Therefore, in this experiment, a step-scan Fourier-transform interferometer was employed to collect the transient infrared difference spectra upon excitation of the sodium nitrite aqueous solution in the absence and presence of methanol or ethanol upon 355 nm pulsed excitation. Coupled with the predicted absolute energies and harmonic wavenumbers using B3LYP density functional theory and aug-cc-pVTZ method with the CPCM model to account for the medium effect of H2O, a transient band at 1860-2030 cm-1 in 1 ms could be attributed to dissolved N2O3 isomers that could be generated from the association reaction of the photolytic intermediates, NO and NO2, in which NO2 can be generated from the rapid reaction of OH and NO2-. After adding a high concentration of alcohols, the depletion rate of N2O3 decelerated slightly. According to the reaction mechanisms and predicted thermodynamics, this might be due to the less reactivity of N2O3 with alcohols compared to water. In addition, comparing the transient population of N2O3 in the absence and presence of CH3OH or C2H5OH, the upper-bound bimolecular rate coefficient of NO or NO2 with alcohols is reported as 7.3 × 103 M-1 s-1. The spectroscopic and kinetic evidence of the reactivity of alcohols with NO, NO2, and N2O3 are provided to augment the roles of alcohols and NxOy in solution or in aqueous aerosol photochemistry.

第一章 緒論 1
1.1 氣溶膠於大氣化學反應之重要性 1
1.1.1 氣溶膠的來源、種類與組成 1
1.1.2 溼氣溶膠提供之反應環境 2
1.2 大氣中亞硝酸根(NO2-)的來源與重要性 2
1.2.1 NO2-於水相的光解 2
1.2.2 OH及NO自由基之重要性與反應 3
1.3 大氣中CH3OH與C2H5OH的來源、重要性及與自由基之反應 4
1.4 研究動機 5
參考文獻 13
第二章 光譜技術原理、實驗系統架設及樣品溶液製備 17
2.1 傅立葉轉換紅外光譜儀 17
2.1.1 麥克森干涉儀 17
2.1.2 單色光與多色光干涉 18
2.1.3 傅立葉轉換 19
2.1.4 截斷函數與削足函數 19
2.1.5 相位誤差與相位校正 21
2.1.6 連續式掃描模式 21
2.2 步進式掃描時間解析傅立葉轉換紅外光譜術 22
2.2.1 工作原理 22
2.2.2 跳點取樣 23
2.2.3 AC/DC耦合數據擷取原理 24
2.3 靜態光譜儀 25
2.3.1 靜態紫外/可見光吸收光譜儀 25
2.3.2衰減全反射式掃描傅立葉轉換紅外光譜儀 25
2.4 時間解析紅外差異吸收光譜之實驗系統架設 26
2.4.1 雷射激發系統 26
2.4.2 樣品推進系統 26
2.4.3 樣品槽 26
2.4.4 步進式掃描時間解析傅立葉轉換紅外光譜儀 26
2.4.5 數據擷取系統 26
2.5 儀器參數設定 27
2.5.1 靜態紫外/可見光吸收光譜儀 27
2.5.2 衰減全反射式掃描傅立葉轉換紅外光譜儀 27
2.5.3 步進式掃描傅立葉轉換紅外光譜儀 28
2.6 樣品溶液製備 30
2.6.1 NaNO2水溶液 30
2.6.2 NaNO2/CH3OH莫耳數20/1、5/1與1/1之混合水溶液 30
2.6.3 NaNO2/C2H5OH莫耳數20/1、5/1與1/1之混合水溶液 30
參考文獻 46
第三章 理論計算 47
3.1 最佳化結構 47
3.2 預測之絕對能量與簡諧振動波數 47
參考文獻 56
第四章 結果與討論 57
4.1 靜態紅外與紫外/可見光吸收光譜 57
4.2 光解NaNO2水溶液之時間解析紅外差異吸收光譜 58
4.3 添加不同濃度CH3OH或C2H5OH之NaNO2水溶液的光解反應 61
4.3.1 時間解析差異吸收光譜 61
4.3.2 動力學分析 62
參考文獻 71
第五章 結論 72
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