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

文献信息

发布日期 2018-02-08
DOI 10.1039/C7CP07311A
影响因子 3.676
作者

Li Liu, Jing Zhang, Shaonan Dong, Fuping Zhang, Ye Wang, Shuping Bi


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摘要

Density functional theory (DFT) calculations combined with cluster models are performed at the B3LYP/6-311+G(d,p) level for investigating the solvent effects in Al(H2O)63+ water-exchange reactions. A “One-by-one” method is proposed to obtain the most representative number and arrangement of explicit H2Os 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 H2Os are added one by one until the inner-sphere is fully hydrogen bonded. Finally, the optimal pathways with Nm′ = 0–7 are obtained. The structural and energetic parameters as well as the lifetimes of the transition states are compared with the results obtained with the “Independent-minimum” method and the “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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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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