【摘要】：1、離子液體以其獨特的性質及廣泛的應用吸引了人們的注意。而氫鍵作為離子液體中一種重要的非共價作用,其數量與強弱將影響離子液體的性質。因此本文將使用量子化學的計算方法對兩種咪唑類陽離子(一甲基咪唑陽離子[Mim]+、1,3-二甲基咪唑陽離子[Mmim]+)及不同的陰離子([NO3]-、[ClO4]-、[BF4]-、[AlCl4]-、[Al2Cl7]-)結合形成的離子對及氫鍵進行研究。(1)在MP2/6-311++G(d,p)理論水平上對一甲基咪唑[Mim]+類復合物([Mim]+[NO3]-、[Mim]+[ClO4]-、[Mim]+[BF4]-、[Mim]+[AlCl4]-、[Mim]+[Al2Cl7]-)進行結構優(yōu)化及性質計算。通過對這些復合物進行結構分析、相互作用能比較、自然鍵軌道(NBO)中的二階微擾能分析、電荷轉移量比較、分子中的原子(AIM)分析,結果表明:a.所有的陰陽離子對之間都發(fā)生了電荷轉移,證明陰、陽離子之間形成氫鍵。b.通過對離子對中形成的氫鍵的平衡距離、二階微擾能E(2)及AIM進行分析和比較,結果表明:質子性的NH···X氫鍵的強度強于非質子性的CH···X氫鍵。c.正負離子間的總相互作用能變化趨勢與氫鍵強弱的順序是一致的,[Mim]+[NO3]-[Mim]+[ClO4]-[Mim]+[BF4]-[Mim]+[AlCl4]-。d.陰離子從側面接觸[Mim]+形成的”side”構象比從上面接觸形成的“top”構象更利于氫鍵的形成。(2)在MP2/6-311++G(d,p)理論水平上對1,3-二甲基咪唑[Mmim]+類復合物([Mmim]+[NO3]-、[Mmim]+[ClO4]-、[Mmim]+[BF4]-、[Mmim]+[AlCl4]-、[Mim]+[Al2Cl7]-)進行結構優(yōu)化及相互作用能計算。通過與一系列的一甲基咪唑[Mim]+類復合物進行對比,結果表明:a.1,3-二甲基咪唑[Mmim]+類復合物的氫鍵均比相應的一甲基咪唑[Mim]+類復合物氫鍵弱,這是因為缺少質子性的N-H鍵的存在。b.[Mmim]+[AlCl4]-的穩(wěn)定構型及相互作用能和化合物[Mmim]+[Al2Cl7]-的很形似,這與[Mim]+[AlCl4]-和[Mim]+[Al2Cl7]-的結論類似。c.氫鍵強弱順序為[Mmim]+[NO3]-[Mmim]+[ClO4]-[Mmim]+[BF4]-[Mmim]+[AlCl4]-,與一甲基咪唑[Mim]+類復合物結論一致。2、本文采用密度泛函理論(DFT),在B3LYP/6-311++G(d,p)理論水平上并結合D3校正研究了不同的陽離子([Mim]+、[Mmim]+)和陰離子([NO3]-、[ClO4]-、[BF4]-、[AlCl4]-、[Al2Cl7]-)及離子對([Mim]+[ClO4]-、[Mmim]+[NO3]-)分別與SO2分子形成復合物的幾何構型及相互作用能。結果表明:SO2與[Mim]+形成一個N-H···O-S和一個C-H···O-S型氫鍵,而與[Mmim]+形成兩個C-H···O-S型氫鍵,兩者作用能相差約14kJ·mol-1。SO2與陰離子NO3-、ClO4-、BF4-、AlCl4-之間通過O-Sδ+···Xδ-型的靜電引力結合,作用力介于38~90 kJ·mol-1。結果表明SO2與陽離子間的C-H···O-S型氫鍵及與陰離子間的靜電引力是咪唑陽離子類離子液體脫硫效果的主要來源。
[Abstract]:1. Ionic liquids have attracted much attention for their unique properties and wide applications. As an important noncovalent interaction in ionic liquids, the amount and strength of hydrogen bonds will affect the properties of ionic liquids. Therefore, two kinds of imidazole cations (Mim, Mmim) and different anions ([NO3] -, [ClO4] -, [BF4] -) and different anions ([NO3] -, [ClO4] -, [BF4] -) are calculated by quantum chemistry. [AlCl4] -, [Al2Cl7] -) binding ion pairs and hydrogen bonds were studied. (1) at the theoretical level of MP2/6-311 G (DNP), the complexes of [Mim] [Mim] class ([Mim] [NO3] -], [Mim] [ClO4] -, [Mim] [BF4] -, [Mim] [AlCl4] -, [Mim] [Al2Cl7] -) for structural optimization and properties calculation. By analyzing the structure of these complexes, comparing the interaction energy, analyzing the second order perturbation energy in the natural bond orbital (NBO), comparing the charge transfer amount, and analyzing the atomic (AIM) in the molecule, the results show that: a. Charge transfer occurs between all pairs of anions and cations, proving that hydrogen bonds are formed between anions and cations. The equilibrium distance of hydrogen bond formed in ion pair, second order perturbation energy E (2) and AIM were analyzed and compared. The results show that the strength of proton NH X hydrogen bond is stronger than that of non proton CH X hydrogen bond. The change trend of total interaction energy between positive and negative ions is consistent with the order of hydrogen bond strength, [Mim] [NO3]-[Mim] [ClO4]-[Mim] [BF4]-[Mim] [AlCl4] -. The "side" conformation formed by the side contact of anions [Mim] is more favorable to the formation of hydrogen bonds than the "top" conformation formed from the above contact. (2) in MP2/6-311 G (d, the formation of hydrogen bonds is more favorable. P) at the theoretical level, the complexes of [Mmim] [NO3] -, [Mmim] [ClO4] -, [Mmim] [BF4] -, [Mmim] [AlCl4]- [Mim] [Al2Cl7] -) structure optimization and interaction energy calculation. Compared with a series of monomethyl imidazole [Mim] complexes, the results show that the hydrogen bonds of A. 1 and 3-dimethyl imidazole [Mmim] complexes are weaker than those of the corresponding Mim complexes. This is due to the absence of proton N-H bonds. The stable configuration and interaction energy of [Mmim] [AlCl4]-is similar to that of compound [Mmim] [Al2Cl7]. This is similar to the conclusion of [Mim] [AlCl4]-and [Mim] [Al2Cl7]. The order of hydrogen bond strength is [Mmim] [NO3]-[Mmim] [ClO4]-[Mmim] [BF4]-[Mmim] [AlCl4] -, which is consistent with the conclusion of a methylimidazole [Mim] class complex. 2. The density functional theory (DFT) (DFT), is used in this paper. Different cations ([Mim], [Mmim]) and anions ([NO3] -, [ClO4] -, [BF4] -, [AlCl4] -, [BF4] -, [AlCl4] -] have been studied at the theoretical level of B3LYP/6-311 G (DNP) and D3 correction. [Al2Cl7] -) and [Mim] [ClO4] -, [Mmim] [NO3] -, respectively. The results show that SO2 forms a N-H O-S and C-H O-S hydrogen bonds with [Mim] and two C-H O-S hydrogen bonds with [Mmim]. The difference of the interaction energy between 14kJ mol-1.SO2 and anionic NO3-,ClO4-,BF4-,AlCl4- is about the interaction of O-S 未 X 未-type electrostatic force between NO3-,ClO4-,BF4-,AlCl4- and O-S 未, and the interaction force is between 38 kJ mol-1. and 90 kJ mol-1.. The results show that the C-H O-S hydrogen bond between SO2 and cations and the electrostatic force between SO2 and anions are the main sources of desulfurization effect of imidazole cationic ionic liquids.
【學位授予單位】：山西師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.1

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