臺灣博碩士論文加值系統

在本文中，我們使用半經驗AM1方法並結合circumscribing algorithm 去檢驗kinetic ring-stacking model，所檢驗的對象有C24 (D6d)、C26 (D3h)、C30 (D5h)、C32 (D3)、C34 (C3V)、C36 (D6h)及C36 (D2d) fullerene cage。根據所得的結果發現當開始堆疊生成新鍵時，前驅物與belt間大都為吸熱反應。而穩定中間物與final belt間為一個放熱反應，即實驗上的退火(Annealing)過程。經由不同小fullerene cage的形變能分析，發現多元環相較於單元環而言，有較高的形變能，因此不利於cage的形成。接著進一步比較並分析不同小fullerene cage的成長過程，發現對於C30 (D5h) fullerene cage而言，均是以多元環當前驅物形成fullerene cage，，在低溫下，具有較高的形變能及較大的活化能，溫度低時不利其越過能量障礙得到bowl-like結構，不利於cage生成。經由C36 (D2d) 和 C36 (D6h) fullerene cage的單元環形成過程，發現C36 (D2d) fullerene在生成過程中，自由能不利的，因此C36 fullerene 是以D6h 的形式存在。最後，經由比較annealing 過程，發現對於單元環而言，生成的相對趨勢為C36 (D6h) > C28 (Td) > C26 (D3h) > C24 (D6d)。對於多元環而言，生成時的相對趨勢為 C36 (D6h) > C32 (D3) > C30 (D5h) > C26 (D3h) > C24 (D6d)。

In this study, a combined quantum mechanical/graph theoretic method has been used to examine the ring-stacking mechanism for the growth of small fullerene cages C2n (n=12-18). It is observed that the reactions between the precursors and the belts in most cases are endothermic, and the reactions between the stable intermediates (bowls) and final belts are exothermic which is akin to the fullerene annealing process. According to the deformation analysis, the monocyclic precursor is found to have lower deformation energies than the polycyclic precursors. The first stacking step of monocyclic precursor (C6) has been examined further by using B3LYP/cc-pVDZ method. Basing on the analysis of the deformation energies and free energies, it is found that C6 stacks with C12 ring is the most feasible path. In addition, based on the deformation energies and free energetic analisys suggest that C36 (D6h) cage formation is kinetically favored than C36 (D2d). According to our analysis of ring stacking model, it is concluded that the relative trend of fullerene formation is C36 (D6h) > C28 (Td) > C26 (D3h) > C24 (D6d) for the monocyclic precursor. In addition, for the bi-cyclic precursor, the relative trend of fullerene formation is C36 (D6h) > C32 (D3) > C30 (D5h) > C26 (D3h) > C24 (D6d)

目 錄
中文摘要 2
英文摘要 3
第一章 緒 論 19
1.1 歷史背景 19
1.2 Fullerene 成長機制的回顧 20
第二章 計 算 方 法 35
2.1 Circumscribing algorithm 35
2.2 量化計算 39
2.3 AM1 40
2.4 Vibrational frequency analysis 40
2.5 形變能 (Deforamtion energy) 42
2.6 計算過程 43
第三章 結 果 與 討 論 46
3.1 C24 (D6d) Fullerene 46
3.2 C26 (D3h) Fullerene 69
3.3 C30 (D5h) Fullerene 95
3.4 C32 (D3) Fullerene 116
3.5 C34 (C3V) Fullerene 173
3.6 C36 (D6h) 和 C36 (D2d) fullerenes 223
3.7 比較不同小Fullerene cages 260
第四章 結 論 278
參 考 文 獻 282

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