二溴一氯甲烷在近紫外光區多光子光解機構之新研究

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姓名

楊士興(Shi-Xing Yang) 查詢紙本館藏

畢業系所

化學學系

論文名稱

二溴一氯甲烷在近紫外光區多光子光解機構之新研究
(Multiphoton photodissociation mechanisms of dibromochloromethane at near ultraviolet wavelengths.)

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★ 以近紫外光光解碘仿及相關分子之光譜研究	★ 266 nm光解碘化甲烷類分子之可見光區放射光譜研究
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★ 高靈敏度溴化亞甲基之分光光譜與溴仿光解之放射光譜研究	★ 266 nm雷射光解溴仿之放射光譜
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摘要(中)

本研究是以 266 nm、280 nm、285 nm、289 nm、355 nm雷射為光解光源，於流動式樣品槽中進行二溴一氯甲烷 (CHBr2Cl) 的光解反應，搭配染料雷射探測其中間產物的雷射誘導螢光分光光譜，並取得各物種的放射光譜。由於先前研究的結果和在其他溴烷類(CHBr3和CHBrCl2) 之研究結果有所不一致，重新以266 nm光解二溴一氯甲烷 (CHBr2Cl) 所得之放射光譜中，可以觀測的物種為 CH (A2Δ,B2Σ-, C2Σ+)，激發態溴原子的躍遷 C2 的 Swan Band。在雷射誘導螢光分光光譜中可以觀測到激發態的 CHCl。利用觀測到物種所做不同功率之雷射光源對訊號放光強度的實驗、改變樣品槽壓力觀測訊號強弱的實驗以及利用不同近紫外光波長光解二溴一氯甲烷之放射光譜的不同，可以更進一步了解二溴一氯甲烷在近紫外光區的光解機制。

摘要(英)

The photolysis at near ultraviolet wavelengths of halomethanes such as dibromochloromethane (CHBr2Cl) is an importance source of bromine atoms that contributes to the stratospheric ozone depletion, but the multiphoton photodissociation mechanisms of CHBr2Cl still remain unclear. Previous study at 266 nm has some results that are inconsistent with the mechanism model for other bromomethanes (CHBr3 and CHBrCl2). In this thesis, we investigated the multiphoton photolysis of CHBr2Cl at 266 nm as well as at other wavelengths (280 nm, 285 nm, 289 nm, and 355 nm). Nascent emission spectra and laser-induced dispersed fluorescence spectra of products or reaction intermediates in these photolysis reactions of CHBr2Cl in a slow flow cell were successfully recorded. Several electronically excited species including CH (A2Δ, B2Σ–, and C2Σ+), C2 (d3Πg), and excited state atomic Br were observed in the nascent emission spectra, while CHCl was successfully found using the laser-induced dispersed fluorescence spectroscopy. More experiments including the concentration dependence and the power dependence were also conducted and these results clarified the multiphoton photolysis mechanism of CHBr2Cl at near ultraviolet wavelengths.

關鍵字(中)

★ 二溴一氯甲烷
★ 雷射
★ 多光子光解機構

關鍵字(英)

★ dibromochloromethane
★ Multiphoton photodissociation mechanisms

論文目次

摘要 (中文) Ⅰ
摘要 (英文) Ⅱ
謝誌 Ⅲ
目錄 Ⅳ
表目錄 Ⅵ
圖目錄 Ⅶ
第一章導論
1-1 研究方向與動機 1
1-2 溴仿、一溴二氯甲烷、二溴一氯甲烷之相關研究 2
1-3 研究目標 8
第二章實驗
2-1 光譜技術的簡介 9
2-2 流動式樣品槽之實驗裝置 11
2-3 光解雷射 12
2-4 增強式電荷偶合裝置偵測器 13
2-5 光解後之放光收集 16
2-6 利用染料雷射激發物種之螢光分光光譜 19
2-6-1 改變樣品槽壓力觀測訊號強弱的關係 19
2-6-2 不同功率之雷射光源對訊號放光強度的關係 20
2-6-3 在不同壓力下改變石榴石雷射與染料雷射兩 20
者的相對延遲時間隊物種訊號放光強度的關係
第三章光解CHBr2Cl之放射光譜與機構探討
3-1 流動式樣品槽內光解二溴一氯甲烷之放射光譜 22
3-1-1如何產生激發態溴原子 25
3-2 266 nm 光解二溴一氯甲烷之中間產物其螢光分光光譜 27
3-2-1 CHCl 物種的螢光分光光譜 28
3-2-2 CHBr 物種的螢光分光光譜 31
3-3 266 nm 光解 CHBrCl 的光解機制 33
3-4 近紫外光 (266 nm、280 nm、285 nm、289 nm)
波長光解CHBr2Cl 之放射光譜探討 35
第四章結論 40
參考文獻 43

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指導教授

張伯琛(Bor-Chen Chang)

審核日期

2009-7-21

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