利用密度泛函理論計算探討RCNC (R=H,F,Cl,Br,CN,NH2,CH3)自由基與NO之反應機制

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Title:	利用密度泛函理論計算探討RCNC (R=H,F,Cl,Br,CN,NH2,CH3)自由基與NO之反應機制 Density functional study on the reaction mechanisms of RCNC(R=H,F,Cl,Br,CN,NH2,CH3) +Radical with NO
Authors:	張奕中 Zhang, Yi Zhong
Contributors:	化學系應用化學碩士班
Keywords:	自由基 RCNC
Date:	2014-12-25
Issue Date:	2015-02-05 10:22:05 (UTC+8)
Abstract:	能源已是世界不可或缺的一部份，工業革命後為了提升生活品質，人們大量的直接或間接使用化石燃料（Fossil fuels），更加速了能源的使用以求文明進步。大量消耗化石燃料導致地球產生嚴重的環境變遷，如COx及NOx等，進而引起全球氣候暖化的溫室效應（Greenhouse Effect），其中NO會產生化學光煙霧也會破壞臭氧層，因此，本論文主要討論自由基RCNC ( R = H、F、Cl、Br、CN、NH2、CH3 )與NO之反應機制之探討。我們使用密度泛函理論計算 (density function theory) 去研究： RCNC ( R = H、F、Cl、Br、CN、NH2、CH3 ) 與 NO的反應機構。我們利用RCNC的碳和NO的氮會產生兩個同分異構物 (Cis、Tran ) 我們使用B3LYP/6-31G做結構最佳化去計算。預測並計算所有的結構並找出最適當的路徑： PATH A: R→IM1→TS1→IM3→TS2→IM4→TS3→P1 PATH B: R→IM2→P2 主要反應路徑為PATH A，在PATH A是經由NO分子上的N原子攻擊RCRNC基上的CR原子且伴隨C−N鍵的斷裂生成產物RCN + NCO (P1)。而速率決定步驟為TS3，推電子取代基( NH2、CH3、H )也較拉電子取代基低了約4.17~10.51 kcal/mol，因此推電子取代基有助於反應發生，我們推測是以CH3推電子基之RCNC有利於與NO的反應。 The nitric oxide (NO) is a notorious compound for polluting environment. Recent year, removing nitric oxide from the atmosphere becomes a focus of the investigation. In our work, we study the RCNC (R= H, F, CI, Br, CN, NH2, CH3) radical reacted with NO molecule with Gaussian 03 program. The reactants, intermediates, transitions states and products have also been optimized at B3LYP/6-31G level. We find two important reaction pathway, PATH A: R→ IM1→ TS1→ IM3 → TS2→ IM4→ TS3→ P1 and PATH B: R→ IM2→ P2. Almost of PATH B is endothermal reaction. Therefore, the PATH A is the major reaction pathway. The rate-determining step in PATH A is the process of the IM3 transfer to TS3. Furthermore, the calculated result also shown the electron donating group could decrease the energy barrier, and the CH3 group is better than others. The electron-withdrawing group would be enhance the energy barriers, and the F group is more strong than others.
Appears in Collections:	[Department of Chemistry & Graduate Institute of Applied Chemistry ] thesis

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