Citation: LI Wei, ZHANG Jing, QI Chuan-Song. Quantum Chemistry Calculations of Ion Cluster Models of EMIM Ionic Liquids[J]. Acta Physico-Chimica Sinica, 2015, 31(9): 1690-1698. doi: 10.3866/PKU.WHXB201507071
EMIM离子液体离子簇模型的量子化学计算
以1-乙基-3-甲基咪唑(EMIM)卤化物、氟硼酸盐、三溴化物和二碘溴酸盐、氯铝酸和溴铝酸盐等不同种类EMIM离子液体为研究对象, 对多阳离子、多阴离子的离子簇模型进行了量子化学计算研究. 首先在B3LYP/6-311++G(d,p)水平上(I使用6-311G(d,p)基组)对{[EMIM]Xn}(n-1)- (X = Cl, Br, I, BF4, AlCl4, AlBr4, Br3,IBrI, FHF; n = 2, 3)和{[EMIM]2Xn'}(n'-2)- (n' = 3, 4, 5)离子簇进行构型优化, 并对卤化物和氟硼酸盐进行了振动光谱计算. 结果表明所采用理论模型在键长、键角等结构参数及红外振动光谱方面均与实验结果符合较好.同时对不同离子簇模型中阴、阳离子间相互作用能与实验熔点之间的关系进行了研究, 发现采用{[EMIM]2Xn'}(n'-2)--模型时EMIM离子液体实验熔点与阴、阳离子间相互作用能之间呈现近线性关系.
English
Quantum Chemistry Calculations of Ion Cluster Models of EMIM Ionic Liquids
Different types of 1-ethyl-3-methylimidazolium (EMIM) ionic liquid compounds, including halides, tetrafluoroborate, tribromide, diiodobromate, chloroaluminate, and bromine aluminate, have been investigated using quantum chemical calculations. First, geometry optimizations of the ion systems, including {[EMIM]Xn}(n-1)- (X = Cl, Br, I, BF4, AlCl4, AlBr4, Br3, IBrI, FHF; n = 2, 3) and {[EMIM]2Xn'}(n'-2)- (n' = 3, 4, 5), were performed using the density functional theory (DFT) B3LYP method together with the 6-311++G(d,p) (6-311G(d,p) for I) basis set. The vibrational spectra were also calculated for the EMIM halides and tetrafluoroborate. The obtained structures and vibrational spectra were consistent with experimental results. In addition, a linear correlation between melting point and interaction energy was obtained for the {[EMIM]2Xn'}(n'-2)- models of the compounds studied.
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Key words:
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Density functional theory
- / Imidazolium ionic liquid
- / Interaction energy
- / Ion cluster
- / Melting point
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