臺灣博碩士論文加值系統

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，但最近亦有研究陽離子中1H及19F 的NMR 光譜論文指出，在不同的溫度及不同的有機溶劑含量下，發現離子液體中，超陰離子（hyper anion preference, HAP）的現象多於超陽離子的情形。
究竟是何者在主導離子液體和溶劑分子間的相對作用，以及超陽子或超陰離子的情形，是本論文所要探討的主要研究動機。我們利用 B3LYP/6-31G* 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 NMR 實驗所得的 1H 及 19F 之T1（遲緩時間）測定的結果。
本論文第一部份（加入溶劑至融鹽系統中）的計算結果與NMR實驗的結果相符，且若將末端碳接三個氫原子的醇類溶劑（簡稱“末端氫未被氟化的醇類”）的末端碳上所接的三個氫原子以三個氟原子取代（簡稱“末端氫被氟化的醇類”），則在整體上看來，對於融鹽系統的結構有穩定的作用。但在將終端碳上接三個氫原子且官能基為 NO2 的溶劑（簡稱“末端氫未被氟化的硝基烷類”）終端碳上的三個氫原子以氟原子取代時（簡稱“末端氫被氟化的硝基烷類”），結果卻有逆轉的趨勢。在論文第二部份（超離子情形）的理論計算結果並無法解釋 NMR 實驗之結果，對此無法解釋的現象我們能以如下的公式來解釋：
�孱 =H－TS ……… (1)
當 G = 0 時，H = TS
�� T = �寒 / �巽 ……… (2)
其中，H 即為理論計算所得的穩定能（SE），但由上面公式(2)可見，溫度 (T) 與亂度 (S) 呈反比，而與 H 呈正比。然而在超陰離子及超陽離子的情形下，H 值並沒有多大的差別，所以我們可以下一個結論：氣態下的離子液體，事實上受到entropy change (熵,S) 的影響較大。

Under the neat ionic liquid condition, it is observed that the cation and anion diffused respectively. In recently, there were also papers about cation’s 1H and 19F NMR spectrum pointed out that the HAP (hyper anion preference) is more than the HCP (hyper cation preference) under the different temperature and the different organic solvent ratio.
Which reason actually affects the intermolecular relative function in the ionic liquid and the solvent? And which reaslly affects the hyper anion preference, is the major research motive of this paper. We use the B3LYP/6-31G* method to calculate the solvent molecule and binding energy tendency between the cation and anion. And using the computational E(2) value to explaine the NMR experimental T1-19F and T1-1H results (relaxation time). The first part of this paper (adding solvents to the ionic liquid system), the computational results meet the NMR experimental results. In the second part of this paper (hyper ion preference), the theoretical calculation results are unable to explain the results of the NMR experiment. Regarding this unable explained phenomenon, we try to use the following formula to explain that,
�� G = H－TS ……… (1)
When G = 0, H = TS
�� T = H/S ……… (2)
Where, H is equal to the theoretical calculated stability energy (SE). In formula 2, the temperature (T) is inverse proportion with entropy change (S) but direct proportion with enthalpy change (H). Thought the calculated H values have not much difference between hyper anion and hyper cation, we explain that regarding the next conclusion: Under the gaseous state ionic liquid, the entropy change (S), in fact, is the most influence.

摘要 I
Abstract III
第一章 緒論..................1
第二章 理論背景..................3
2-1 離子液體簡介..................3
2-1-1 研究目的..................6
2-2 氫鍵..................7
2-3 計算理論..................10
2-3-1 HF理論方法..................10
2-3-2 DFT 理論方法..................11
2-3-3 基底..................13
2-3-4 分裂 (split) 基底..................13
2-3-5 極化函數 ( polarization function )........14
2-3-6 擴散函數 ( diffuse function )..................15
2-4 天然鍵性軌域 48-49..................15
第三章 計算方法..................19
3-1 選用軟體..................19
3-2 採用的計算條件..................19
3-3 計算流程..................20
3-3-1 計算指令..................21
3-3-2 幾何最佳化的目的..................21
第四章 結果與討論..................24
4-1 不同的融鹽系統..................24
4-2 融鹽陰、陽離子與溶劑間的作用.................25
4-2-1 EMI+-solvent & BMI+-solvent..................26
4-2-2 solvent-BF4- & solvent-PF6-..................26
4-3 融鹽陰陽離子對與溶劑間的理論計算.............27
4-4 融鹽陰、陽離子及陰陽離子對與溶劑間的作用之探討..27
4-4-1 由結構形態來探討..................28
4-4-2 由穩定能來探討..................29
4-4-2-1 溶劑與融鹽陰離子或陽離子結合..................29
4-4-2-2 溶劑與融鹽陰陽離子對結合..................30
4-4-3 由 E(2) 值來探討..................32
4-4-3-1 溶劑與融鹽陰離子或陽離子結合..................32
4-4-3-2 溶劑與陰陽離子對結合..................34
4-4-4 與 NMR 實驗結果之比較..................39
4-4-5 小結..................40
4-5 融鹽超離子現象之探討..................45
4-5-1 探討緣起..................45
4-5-2 超陰離子..................47
4-5-3 超陽離子..................48
第五章 結論..................50

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