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題名 | Theoretical Study of the Cyclo Addition Reactions of the Weakly Bound Molecular Trimers=弱結合三聚體分子環化加成反應之理論研究 |
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作 者 | 陳成; 劉敏憲; 鄭根發; 徐雙富; | 書刊名 | 中正嶺學報 |
卷期 | 32:2(A) 民93.05 |
頁次 | 頁91-108 |
分類號 | 346.2 |
關鍵詞 | 弱結合三聚體; 環化加成反應; B3LYP型6-311++G(3df,2pd)基底函數; Weakly bound complexes (C[feaf]H[feaf])[feb0]; (HCN)[feb0]and (FCN)[feb0]trimers; Cyclo-addition reactions; B3LYP/6-311+G(2d,p); B3LYP/6-311++G(3df,2pd); |
語文 | 英文(English) |
中文摘要 | 本研究以多種 DFT、ab initio 及半經驗分子軌域理論模擬獲得 (C[]H[])[]、(FCN)[]及 (FCN)[]等分子的穩定態極小值位能。藉由這些理論計算方法,同時探討前述弱結合三聚體 (weakly bound trimer) 及其相關芳香六環型分子環化加成聚合之反應機構。吾人檢視計算與實驗所獲數值,發覺 DFT 理 論 B3LYP 型含 6.311++G(3df,2pd) 基底函數的方法對 3 分子C[]H[]比聚合形成苯之 △H[],△G[]及3分子HCN 聚合形成 1,3,5-三氮井 (1,3,5-triazine) 之 △H[]的計算結果最接近實驗值。從所有的計算結果中,均證實不論由分子單體聚合形成芳香環型分子抑或由弱結合三眾體轉變形成芳香環型分子,兩種途徑之過渡狀態相當近似。比較上述反應之位能曲線,反應由 3FCN=(FCN)[]=C[]F[]N[]所需活化能最低,而反應由 3C[]H[]=(C[]H[])[]=C[]H[]所需活化能最高。 |
英文摘要 | Minima on the potential energy surfaces of (C2H2)3, (HCN)3 and (FCN)3 have been located by various type of the DFT, ab initio and semi-empirical MO methods. With the various theoretical methods, the cyclo-addition type isomerization reaction between these weakly bound trimers and their related aromatic six-menbered ring type of molecules were also studied. All of these cyclization type reactions belong to the exothermic ones in nature. By checking the calculated and the observed ΔH° and ΔG° between benzene and 3 moles of C2H2 , and ΔH° between 1,3,5-triazine and 3 moles HCN, it was found that DFT method with B3LYP/6-311++G(3df,2pd) type basis gives the best results. The transition states of the above mentioned reactions have been all found by the selected methods. From various computational results, it proves that all the transition states between the monomers and the aromatic molecules are exactly identical to the transition states between the related weakly bound trimers and the same aromatic molecules. By comparison the potential curves of the above mentioned reactions, it shows that 3FCN = (FCN)3 = C3F3N3 requires the lowest activation energy and 3C2H2 = (C2H2)3 = C6H6 requires the highest activation energy. |
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