臺灣博碩士論文加值系統

我們利用B3LYP/6-31G*的方法計算EMI-Cl、 EMI-Br、 EMI-BF4 和EMI-PF6 的結構和性質，且對EMI+ 環上的酸性氫作一探討。並利用 Weinhold 所提出對氫鍵的看法 ”氫鍵是由Hyperconjugation 和 Rehybridization 兩種效應達成一穩定的平衡狀態”　的觀點來解釋在離子液體裡的氫鍵現象

　 在純離子液體狀態下，可以觀察到陰陽離子各自擴散的情形，但加入不同的有機溶劑之後，發現離子液體和溶劑分子間有著不同程度的相對作用，且最近亦有研究陽離子中15N NMR 光譜論文指出，溶劑分子和陰離子間的作用，主導離子液體和溶劑分子間的相對作用。我們利用 B3LYP/3-21G* 的方法來計算溶劑分子和陰陽離子間的結合能傾向，並利用計算所得的 E(2) 值來解釋實驗所測得的19F NMR光譜的現象。

Bond orbital analysis performed on EMI+ and various Lewis bases reveals that the Weinhold’s “counterbalance effects of rehybridization and hyperconjugation” are valid for the most polar C-H (EMI+) bonding orbitals and are not suitable for the lone-pair bonding orbital of the bases. Only when alkyl C-H BOs are involved in hyperconjugative interactions with the base, chloride or bromide anions under this research, the hyperconjugation effect prevails over rehybridization effect and H-bonding results in a strengthened C(3)-H bond.

The self-diffusing BMI-PF6 in neat ionic liquid (IL) state have been found, in the presence of aprotic organic solvent (AOS), associated to different extents, which can be explained by B3LYP/3-21G* calculated binding energies for the adducts of AOS and PF6 anion. These results are consistent with the very recent nitrogen NMR studies performed on ionic liquids, which infer that solvent-anion interactions dominate modified physical properties. The NBO second-order perturbation energy analysis provides orbital-based explanations for the unusually up-field shifts of 19F NMR resonances in propylene carbonate and the relative solvent-IL effects .

目錄

摘要...........................................I
Abstract.......................................II
誌謝...........................................III
目錄...........................................IV
表目錄.........................................VII
圖目錄.........................................IX
第一章　緒論...................................1
第二章　理論背景...............................3
　2-1 室溫融鹽簡介............................3
2-1-1 研究目的................................5
2-2 氫鍵......................................5
2-3 計算理論..................................8
2-3-1 HF理論方法..............................8
2-3-2 DFT 理論方法............................9
2-3-3 基底....................................11
2-3-4 分裂 (split) 基底.......................12
2-3-5 極化函數 ( polarization function )......12
2-3-6 擴散函數 ( diffuse function )...........13
2-4 天然鍵性軌域..............................13
第三章　計算方法...............................18
3-1 選用軟體..................................18
3-2 採用的計算條件............................18
3-3 計算流程..................................19
3-3-1 計算指令................................20
3-3-2 幾何最佳化的目的........................21
第四章 結果與討論............................23
4-1 對於氫鍵的探討............................23
4-2 對於EMI‧Cl & EMI‧Br的探討...............26
4-2-1 最佳化結構 & 穩定能.....................27
4-2-2 E(2) 值分析 & C－H 中 C 的 S-character 變化.............................................31
4-3 EMI+與多個陰離子作用......................35
4-3-1 EMI‧2Cl & EMI‧3Cl.....................35
4-3-2 EMI‧2Br & EMI‧3Br.....................38
4-4 EMI‧BF4 & EMI‧PF6.......................40
4-4-1 最佳化結構 & 穩定能.....................41
4-5 關於EMI+ with Cl-、Br-、BF4-、PF6-的結論..46
4-6 BMI-PF6 與溶劑間的作用....................48
4-6-1 BMI-PF6 與溶劑間的作用..................49
4-6-2 BMI+-solvent & solvent- PF6-............50
4-6-3 BMI-PF6 with AN.........................55
4-6-4 BMI-PF6 with DMF........................57
4-6-5 BMI-PF6 with DMSO.......................59
4-6-6 BMI-PF6 with PC.........................62
4-6-7四種溶劑的比較............................64
第五章　結論...................................71
參考文獻.......................................72

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