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水溶液中Al3+第三水化层对Al(H2O)63+水交换特性影响的密度泛函理论研究

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侯晓霞, 董绍楠, 张婧, 毕树平. 水溶液中Al3+第三水化层对Al(H2O)63+水交换特性影响的密度泛函理论研究[J]. 环境化学, 2016, 35(2): 246-253. doi: 10.7524/j.issn.0254-6108.2016.02.2015080101
引用本文: 侯晓霞, 董绍楠, 张婧, 毕树平. 水溶液中Al3+第三水化层对Al(H2O)63+水交换特性影响的密度泛函理论研究[J]. 环境化学, 2016, 35(2): 246-253. doi: 10.7524/j.issn.0254-6108.2016.02.2015080101
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HOU Xiaoxia, DONG Shaonan, ZHANG Jing, BI Shuping. Density functional theory study of the influences of the third hydration shell on the characteristics for the water-exchange reactions of Al(H2O)63+(aq) in aqueous solution[J]. Environmental Chemistry, 2016, 35(2): 246-253. doi: 10.7524/j.issn.0254-6108.2016.02.2015080101
Citation: HOU Xiaoxia, DONG Shaonan, ZHANG Jing, BI Shuping. Density functional theory study of the influences of the third hydration shell on the characteristics for the water-exchange reactions of Al(H2O)63+(aq) in aqueous solution[J]. Environmental Chemistry, 2016, 35(2): 246-253. doi: 10.7524/j.issn.0254-6108.2016.02.2015080101
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水溶液中Al3+第三水化层对Al(H2O)63+水交换特性影响的密度泛函理论研究

  • 1.

    南京大学化学化工学院, 南京, 210023

  • 基金项目:

    国家自然科学基金(21177054)资助.

Density functional theory study of the influences of the third hydration shell on the characteristics for the water-exchange reactions of Al(H2O)63+(aq) in aqueous solution

  • 1.

    School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China

  • Fund Project: Supported by the National Natural Science Foundation of China(21177054).

  • 摘要: 针对水溶液中铝离子第三水化层(hydration shell)对Al(H2O)63+动态水交换反应特性的影响,本文采用密度泛函理论(Density functional theory, DFT)在B3LYP/6-311+G(d,p)基组水平上进行了研究.探讨了第三水化层对第一到第二水化层水交换反应速率常数kex1-2以及第二到三水化层水交换反应速率常数kex2-3的影响.研究结果表明,在第三水化层添加不同数目水分子时相应于kex1-2和kex2-3的活化能垒变化均不大,表明第三水化层对水交换反应速率常数kex1-2和kex2-3影响不大,采用第二水化层就可以较好处理Al(H2O)63+的真实溶剂效应.
    Abstract: The influences of the third hydration shell on the dynamic characteristics for the water-exchange reactions of Al(H2O)63+(aq) complexes in aqueous solution were investigated by density functional theory(DFT) calculations on the basis of B3LYP/6-311+G(d,p). The effects of the third hydration shell on the water-exchange reaction rate constant between the first and second hydration shells kex1-2 and the water exchange rate constant between the second and third hydration shells kex2-3 were examined. DFT calculation results show that the activation energy barriers for both kex1-2 and kex2-3 changes only slightly when different number of water molecules were considered in the third hydration shell. This indicates that the third hydration shell has little influence on the water-exchange rate constants kex1-2 and kex2-3. It is satisfactory to account the explicit solvent effects with two hydration shells for Al(H2O)63+(aq) complexes in aqueous solution.
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  • [1] WILKINS D M, MANOLOPOULOS D E, DANG L X. Nuclear quantum effects in water exchange around lithium and fluoride ions[J]. The Journal of Chemical Physics, 2015, 142(6):064509(1-11).
    [2] HAGVALL K, PERSSON P, KARLSSON T. Spectroscopic characterization of the coordination chemistry and hydrolysis of gallium(Ⅲ) in the presence of aquatic organic matter[J]. Geochimica et Cosmochimica Acta, 2014, 146:76-89.
    [3] VAN ELDIK R. Fascinating inorganic/bioinorganic reaction mechanisms[J]. Coordination Chemistry Reviews, 2007, 251(13-14):1649-1662.
    [4] CASEY W H, RUSTAD J R. Reaction dynamics,molecular clusters,and aqueous geochemistry[J]. Annual Review of Earth and Planetary Sciences, 2007, 35:21-46.
    [5] HUGI-CLEARY D, HELM L, MERBACH A E. Variable-temperature and variable-pressure 17O-NMR study of water exchange of hexaaquaaluminium(Ⅲ)[J]. Helvetica Chimica Acta, 1985, 68(3):545-554.
    [6] FIAT D, CONNICK R E. Oxygen-17 magnetic resonance studies of ion solvation. The hydration of aluminum(Ⅲ) and gallium(Ⅲ) ions[J]. Journal of the American Chemical Society, 1968, 90(3):608-615.
    [7] QIAN Z S, FENG H, YANG W J,et al. Supermolecule density functional calculations on the water exchange of aquated Al(Ⅲ) species in aqueous solution[J]. Chemical Communications, 2008, 33:3930-3932.
    [8] HOFER T S, RANDOLF B R, RODE B M,et al. The influence of quantum forces on molecular dynamics simulation results for hydrated aluminium(Ⅲ)[J]. Chemical Physics Letters, 2006, 422(4-6):492-495.
    [9] MARTÍNEZ J M, PAPPALARDO R R, MARCOS E S. First-principles ion-water interaction potentials for highly charged monatomic cations. Computer simulations of Al3+,Mg2+,and Be2+ in water[J]. Journal of the American Chemical Society, 1999, 121(13):3175-3184.
    [10] BERET E C, GALBIS E, PAPPALARDO R R,et al. Opposite effects of successive hydration shells on the aqua ion structure of metal cations[J]. Molecular Simulation, 2009, 35(12-13):1007-1014.
    [11] BYLASKA E J, VALIEV M, RUSTAD J R,et al. Structure and dynamics of the hydration shells of the Al3+ ion[J]. The Journal of Chemical Physics, 2007, 126(10):2033-2034.
    [12] BOCK C W, MARKHAM G D, KATZ A K,et al. The arrangement of first-and second-shell water molecules in trivalent aluminum complexes:Results from density functional theory and structural crystallography[J]. Inorganic Chemistry, 2003, 42(5):1538-1548.
    [13] SHI W J, JIN X Y, DONG S N,et al. Theoretical investigation of the thermodynamic structures and kinetic water-exchange reactions of aqueous Al(Ⅲ)-salicylate complexes[J]. Geochimica et Cosmochimica Acta, 2013, 121:41-53.
    [14] JIN X Y, YAN Y, SHI W J,et al. Density functional theory studies on the structures and water-exchange reactions of aqueous Al(Ⅲ)-oxalate complexes[J]. Environmental Science and Technology, 2011, 45(23):10082-10090.
    [15] EVANS R J, RUSTAD J R, CASEY W H. Calculating geochemical reaction pathways-exploration of the inner-sphere water exchange mechanism in Al(H2O)3+6(aq)+nH2O with ab initio calculations and molecular dynamics[J]. The Journal of Physical Chemistry A, 2008, 112(17):4125-4140.
    [16] HANAUER H, PUCHTA R, CLARK T,et al. Searching for stable、five-coordinate aquated Al(Ⅲ) species. Water exchange mechanism and effect of pH[J]. Inorganic Chemistry, 2007, 46(4):1112-1122.
    [17] BLEUZEN A, FOGLIA F, FURET E, et al. Second coordination shell water exchange rate and mechanism:Experiments and modeling on hexaaquachromium(Ⅲ)[J]. Journal of the American Chemical Society, 1996, 118(50):12777-12787.
    [18] YANG T X, TSUSHIMA S, SUZUKI A. Quantum mechanical and molecular dynamical simulations on Thorium(Ⅳ) hydrates in aqueous solution[J]. The Journal of Physical Chemistry A, 2001, 105(45):10439-10445.
    [19] YANG T X, BURSTEN B E. Speciation of the curium(Ⅲ) ion in aqueous solution:A combined study by quantum chemistry and molecular dynamics simulation[J]. Inorganic Chemistry, 2006,45(14):5291-5301.
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  • 收稿日期:  2015-08-01
  • 刊出日期:  2016-02-15

水溶液中Al3+第三水化层对Al(H2O)63+水交换特性影响的密度泛函理论研究

  • 1. 南京大学化学化工学院, 南京, 210023
  • 收稿日期:  2015-08-01
基金项目:

国家自然科学基金(21177054)资助.

摘要: 针对水溶液中铝离子第三水化层(hydration shell)对Al(H2O)63+动态水交换反应特性的影响,本文采用密度泛函理论(Density functional theory, DFT)在B3LYP/6-311+G(d,p)基组水平上进行了研究.探讨了第三水化层对第一到第二水化层水交换反应速率常数kex1-2以及第二到三水化层水交换反应速率常数kex2-3的影响.研究结果表明,在第三水化层添加不同数目水分子时相应于kex1-2和kex2-3的活化能垒变化均不大,表明第三水化层对水交换反应速率常数kex1-2和kex2-3影响不大,采用第二水化层就可以较好处理Al(H2O)63+的真实溶剂效应.

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