| Li2SO4溶液中离子间的缔合相互作用:基于密度泛函理论和分子动力学模拟的研究 |
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| 引用本文： | 胡俊,夏斐斐,杨凤丽,郑纯智,房春晖,曾德文,易海波.Li2SO4溶液中离子间的缔合相互作用:基于密度泛函理论和分子动力学模拟的研究[J].盐湖研究,2018,26(1):39-47. |
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| 作者姓名： | 胡俊 夏斐斐 杨凤丽 郑纯智 房春晖 曾德文 易海波 |
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| 作者单位： | 江苏理工学院化学与环境工程学院;中国科学院青海盐湖研究所中国科学院盐湖资源综合高效利用重点实验室;中南大学化学化工学院;湖南大学化学化工学院 |
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| 基金项目： | 国家自然科学(21406020) |
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| 摘 要： | 基于密度泛函理论,使用B3LYP/aVDZ方法对Li_2SO_4(H_2O)_n]~0(n=0~10、18)水合团簇的结构和性质进行了系统地研究,并结合Car-Parrinello分子动力学(CPMD)模拟了不同浓度的Li_2SO_4溶液结构,目的在于理解在Li_2SO_4溶液中离子间缔合相互作用及可能存在的物种。研究发现,对于Li_2SO_4(H_2O)_n]~0(n=0~10、18)水合团簇,双配位单齿螯合接触离子对结构比双配位双齿螯合接触离子对结构更稳定,溶剂共享离子对结构最不稳定。同时,CPMD模拟结果表明,在3.09和3.17 mol/kg的Li_2SO_4溶液中,双配位单齿螯合接触离子对结构仍然是主要物种。以上结果表明在饱和的Li_2SO_4溶液(3.16 mol/kg)中,Li~+和SO_4~(2-)离子间的相互缔合作用主要以双配位单齿螯合接触离子对结构的物种存在,而具有双配位双齿螯合离子对结构的物种占少数,溶剂共享离子对结构几乎不存在。
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| 关 键 词： | 离子缔合 离子水合 接触离子对 溶剂共享离子对 密度泛函理论 分子动力学模拟 |
| 收稿时间： | 2017/4/11 0:00:00 |
| 修稿时间： | 2017/5/10 0:00:00 |
Ions-associated Interaction in Li2SO4 Aqueous Solution:A Density Functional Theory and Molecular Dynamics Simulations Investigation |
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| XIA Fei-fei,HU Jun,YANG Feng-li,ZHENG Chun-zhi,FANG Chun-hui,ZENG De-wen and YI Hai-bo.Ions-associated Interaction in Li2SO4 Aqueous Solution:A Density Functional Theory and Molecular Dynamics Simulations Investigation[J].Journal of Salt Lake Research,2018,26(1):39-47. |
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| Authors: | XIA Fei-fei HU Jun YANG Feng-li ZHENG Chun-zhi FANG Chun-hui ZENG De-wen and YI Hai-bo |
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| Institution: | School of Chemical and Environmental Engineering, Jiangsu University of Technology, Changzhou,213001, China,School of Chemical and Environmental Engineering, Jiangsu University of Technology, Changzhou,213001, China,School of Chemical and Environmental Engineering, Jiangsu University of Technology, Changzhou,213001, China,School of Chemical and Environmental Engineering, Jiangsu University of Technology, Changzhou,213001, China,Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Resources,Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining, Qinghai 810008,China,College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, China and College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan 410082, China |
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| Abstract: | In this paper, the structures and properties of Li2SO4(H2O)n]0 (n = 0-10, 18) hydrated clusters have been systematically investigated by B3LYP/aVDZ methods based on density functional theory to understand the ion-associated interactions and the main species in Li2SO4 aqueous solution. Meanwhile, the Li2SO4 aqueous solutions in different concentrations have been also studied using Car-Parrinello molecular dynamics (CPMD) simulation. It is noted that bis-bidentate contact ion pairs are less stable than bis-monodendate contact ion pairs for Li2SO4(H2O)n]0 (n = 4-10, 18, and the solvent-shared ion pairs are the least stable structures. Meanwhile, the CPMD simulation results show that bis-monodendate contact ion pairs are the main species in 3.09 and 3.17 mol/kg Li2SO4 aqueous solutions. It could be considered that the ions-associated interaction between Li+ and SO42- exists mainly as bis-monodendate contact ion pairs in saturated Li2SO4 aqueous solution (3.16 mol/kg), while bis-bidentate contact ion pairs are of minority, solvent-shared ion pairs can be almost neglected. |
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| Keywords: | Ion association Ion hydration Contact ion pairs Solvent-shared ion pairs Density functional theory Molecular dynamics simulation |
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