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Density functional theory studies on solvent effect in Al(H2O)63+ water-exchange reactions: The number and arrangement of outer-sphere water molecules

Abstract

Density functional theory (DFT) calculations combined with cluster model are performed at B3LYP/6-311+G(d,p) level for investigating the solvent effects in Al(H2O)63+ water-exchange reactions. The “One-by-one” method is proposed to obtain the most representative number and arrangement of explicit H2O in the second hydration sphere. First, all the possible ways to locate one explicit H2O in second sphere (Nm’ = 1) based on the gas phase structure (Nm’ = 0) are examined, and the optimal pathway (with the lowest energy barrier) for Nm’ = 1 is determined. Next, more explicit H2O are added one by one until the inner-sphere is fully hydrogen bonded. The optimal pathways with Nm’ = 0 ~ 7 are obtained finally. The structural and energetic parameters as well as the lifetimes of transition states are compared with the results obtained with “Independent-minimum” method and “Independent-average” method, and all three methods show that the pathway with Nm’ = 6 may be representative. Our results give a new idea for finding the representative pathway for water-exchange reactions in other hydrated metal ion systems.

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Publication details

The article was received on 29 Oct 2017, accepted on 06 Feb 2018 and first published on 08 Feb 2018


Article type: Paper
DOI: 10.1039/C7CP07311A
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    Density functional theory studies on solvent effect in Al(H2O)63+ water-exchange reactions: The number and arrangement of outer-sphere water molecules

    S. Bi, L. Liu, J. Zhang, S. Dong, F. Zhang and Y. Wang, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C7CP07311A

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