针对水溶液中铝离子第三水化层(hydration shell)对Al(H2O)3+6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k1-2ex以及第二到三水化层水交换反应速率常数2-3ex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k1-2ex和k2-3ex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k1-2ex和k2-3ex影响不大,采用第二水化层就可以较好处理Al(H2O)3+6的真实溶剂效应.
参考文献
| [1] | Wilkins, David M.;Manolopoulos, David E.;Dang, Liem X..Nuclear quantum effects in water exchange around lithium and fluoride ions[J].The Journal of Chemical Physics,20156(6) |
| [2] | Hagvall, Kristoffer;Persson, Per;Karlsson, Torbjorn.Spectroscopic characterization of the coordination chemistry and hydrolysis of gallium(III) in the presence of aquatic organic matter[J].Geochimica et Cosmochimica Acta: Journal of the Geochemical Society and the Meteoritical Society,2014:76-89. |
| [3] | Rudi van Eldik.Fascinating inorganic/bioinorganic reaction mechanisms[J].Coordination chemistry reviews,200713/14(13/14):1649-1662. |
| [4] | Casey WH;Rustad JR.Reaction dynamics, molecular clusters, and aqueous geochemistry[J].Annual Review of Earth and Planetary Sciences,20070(0):21-46. |
| [5] | Qian ZS;Feng H;Yang WJ;Miao Q;He L;Bi SP.Supermolecule density functional calculations on the water exchange of aquated Al(III) species in aqueous solution[J].Chemical communications,200833(33):3930-3932. |
| [6] | Hofer TS;Randolf BR;Rode BM.The influence of quantum forces on molecular dynamics simulation results for hydrated aluminium(III)[J].Chemical Physics Letters,20064-6(4-6):492-495. |
| [7] | Martinez, Jose M.;Sanchez Marcos, Enrique;Pappalardo, Rafael R..First-principles ion-water interaction potentials for highly charged monatomic cations. Computer simulations of Al~(3+), Mg~(2+), and Be~(2+) in water[J].Journal of the American Chemical Society,199913(13):3175-3184. |
| [8] | Elizabeth C. Beret;Elsa Galbis;Rafael R. Pappalardo;Enrique Sanchez Marcos.Opposite effects of successive hydration shells on the aqua ion structure of metal cations[J].Molecular simulation,200912/13(12/13):1007-1014. |
| [9] | Bylaska EJ;Valiev M;Rustad JR;Weare JH.Structure and dynamics of the hydration shells of the Al3+ ion[J].The Journal of Chemical Physics,200710(10):4505-1-4505-8-0. |
| [10] | Bock CW.;Markham GD.;Katz AK.;Glusker JP..The arrangement of first- and second-shell water molecules in trivalent aluminum complexes: Results from density functional theory and structural crystallography[J].Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics,20035(5):1538-1548. |
| [11] | Shi, W.;Jin, X.;Dong, S.;Bi, S..Theoretical investigation of the thermodynamic structures and kinetic water-exchange reactions of aqueous Al(III)-salicylate complexes[J].Geochimica et Cosmochimica Acta: Journal of the Geochemical Society and the Meteoritical Society,2013:41-53. |
| [12] | Xiaoyan Jin;Yu Yan;Wenjing Shi.Density Functional Theory Studies on the Structures and Water-Exchange Reactions of Aqueous AI(III)-Oxaiate Complexes[J].Environmental Science & Technology: ES&T,201123(23):10082-10090. |
| [13] | Evans RJ;Rustad JR;Casey WH.Calculating geochemical reaction pathways - Exploration of the inner-sphere water exchange mechanism in Al(H2O)(6)(3+)(aq)+nH(2)O with ab initio calculations and molecular dynamics[J].The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory,200817(17):4125-4140. |
| [14] | Hanauer H;Puchta R;Clark T;van Eldik R.Searching for stable, five-coordinate aquated Al(III) species. Water exchange mechanism and effect of pH[J].Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics,20074(4):1112-1122. |
| [15] | A. Bleuzen;F. Foglia;E. Furet;L. Helm;A. E. Merbach;J. Weber.Second Coordination Shell Water Exchange Rate and Mechanism: Experiments and Modeling on Hexaaquachromium(III)[J].Journal of the American Chemical Society,199650(50):12777-12787. |
| [16] | Tianxiao Yang;Satoru Tsushima;Atsuyuki Suzuki.Quantum Mechamical and Molecular Dynamical Simulations on Thorium(IV) Hydrates in Aqueous Solution[J].The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory,200145(45):10439-10445. |
| [17] | Yang T;Bursten BE.Speciation of the curium(III) ion in aqueous solution: A combined study by quantum chemistry and molecular dynamics simulation[J].Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics,200614(14):5291-5301. |
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