臺灣博碩士論文加值系統

本論文研究分為三部分，在第一章中，我們以高階全初始法CCSD(T) 理論，配合Dunning’s Correlation Consistent Basis Sets (aug-cc-pVnZ, n = D, T, Q)，計算了含有惰性氣體的陰離子 FNgO 的結構與能量，以及解離成 F + Ng + O，F + Ng + O，與OF + Ng等反應路徑的能量。計算結果顯示，singlet state的FNgO在位能面上是很深的能量local minima，並且具有相當大的S-T energy gap，同時對於解離成 OF + Ng的反應也有相當高的能量障礙。這種特殊的穩定性是來自於 ion-induced Ng=O 鍵的生成。計算的結果指出，這類型的陰離子，甚或是一些相關的”離子化合物”，在實驗上可能可以在低溫的環境下被鑑定出來。

在第二章，我們以MP2及CCSD(T)的理論方法配合6-311+G*及aug-cc-pVTZ的基底函數來研究HNBNgF ( Ng = Ar, Kr, Xe ) 這類型惰性氣體分子的穩定性。在最高階的理論方法下，我們發現針對HNBNgF → HNB + Ng + F及HNBNgF → HNBF + Ng兩種反應，HNBArF的反應能量為 7.4 及 -151.5 kcal/mol，能量障礙為14.9及18.6 kcal/mol；HNBKrF的反應能量為14.9及-136.1 kcal/mol，能量障礙為24.5及45.7 kcal/mol；HNBXeF的反應能量為51.7及-107.4 kcal/mol，能量障礙為31.7及62.7 kcal/mol。電荷分佈的分析發現，Ng−B為共價鍵特性，而F−Ng為離子鍵特性。計算結果指出HNBNgF應該都是動力學上穩定的惰性氣體分子。

在第三章中，我們針對芳香性雜五環中的furan的衍生物：2,5-X2-furan、3,4-X2-furan、以及X4-furan (X = Me, Cl, Br, OMe)與甲基乙烯酮 (methyl vinyl ketone, MVK) 所進行的Diels-Alder反應做了一系列的探討。由計算結果發現，如果furan接上拉電子基，其Diels-Alder的反應能量會較為放熱，但是能量障礙也略為增加；而當furan接上推電子基時對反應能量的效應與拉電子基剛好相反，能量障礙的變化卻未如預期般地降低，我們推測這是立體障礙造成的影響。

In chapter one, the structures and energies of the noble-gas containing anions FNgO (Ng = Kr, Xe) have been calculated by high-level ab initio calculation. The FNgO were found to be deep energy minima at the singlet electronic state and their energies are significantly lower than those at the triplet state. High dissociation energy barriers to Ng + OF were also predicted. The unexpected stability of the FNgO was due to the dramatic ion-induced O=Ng bond formation. The calculated results suggested possible experimental identification of the anionic species and even some related “ionic compounds” under cryogenic conditions.

In chapter two of this thesis, high-level electronic structure calculation has been performed on the noble-gas molecules HNBArF, HNBKrF, and HNBXeF. The energetics of the two unimolecular dissociation pathways, (1) HNBNgF → HNB + Ng + F, and (2) HNBNgF → HNBF + Ng, were also calculated. The B–Ng bonds were calculated to be 1.7–2.5  and were found to be covalent in nature. Highly positive charges were assigned to H, B and Ng atoms and highly negative charges to N and F atoms. Both unimolecular dissociation pathways were found to have high energy barriers (>15 kcal/mol), and thus suggests that HNBNgF are dynamically stable species.

In chapter three, we have studied the Diels-Alder reactions of the furan derivatives－2,5-X2-furan, 3,4-X2-furan, and X4-furan (X = Me, Cl, Br, OMe) －with methyl vinyl ketone. The result indicated if the X groups are electron withdrawing, the reactions are more exothermic and have higher energy barriers. If the X groups are electron donating, the reactions are more endothermic, and the barriers are also higher, probably due to steric effects.

中文摘要………………………………………………………………..iii
英文摘要………………………………………………………………...v
第一章 含鈍氣陰離子FNgO- (Ng = Kr, Xe ) 的理論預測

1.1 前言…………………………………………………………..1-2
1.2 計算方法……………………………………………………..1-4
1.3 結果與討論…………………………………………………..1-5
1.4 結論………………………………………………………......1-9
參考文獻………………………………………………………...1-11
圖表……………………………………………………………...1-14

第二章 新型惰性氣體分子 HNBNgF (Ng = Ar, Kr, Xe) 的理論預測
2.1 前言…………………………………………………………..2-2
2.2 計算方法……………………………………………………..2-3
2.3 結果與討論…………………………………………………..2-4
2.4 結論…………………………………………………………..2-8
參考文獻………………………………………………………...2-10
圖表……………………………………………………………...2-13

第三章 Furan衍生物與MVK進行Diels-Alder反應之理論模擬
3.1 前言…………………………………………………………..3-2
3.2 計算方法……………………………………………………..3-3
3.3 結果與討論…………………………………………………..3-3
3.4 結論…………………………………………………………..3-5
參考文獻………………………………………………………….3-7
圖表……………………………………………………………...3-10

第一章
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第二章
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21. (a)王星勳碩士論文”有機鎢金屬路易士酸對弗瑞迪-克拉夫茲及醛類分子 [2+2+2] 環化反應的催化活性探討”，中正大學化學研究所，2000。(b)游茹閔碩士論文”芳香性雜五元環 (pyrrole、furan、thiophen) 與甲基乙烯酮分別進行Diels-Alder與Friedel-Crafts反應之研究”，中正大學化學研究所，2001。(c)蔡麗昭碩士論文”Diels-Alder反應之理論研究”，中正大學化學研究所，2000。