Density functional theory studies on the solvent effects in Al(H2O)63+ water-exchange reactions: the number and arrangement of outer-sphere water molecules. Issue 10 (27th February 2018)

• Record Type: Journal Article
• Authors: Liu, Li; Zhang, Jing; Dong, Shaonan; Zhang, Fuping; Wang, Ye; Bi, Shuping
• Is Part Of: Physical chemistry chemical physics. Volume 20:Issue 10(2018)
• Page Start: 7342
• Page End: 7350
• Publication Date: 2018-02-27
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c7cp07311a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The most representative pathway with N m ′ = 6 for the water-exchange reactions in Al(H2 O)6 3+ is obtained by the "One-by-one" method. Abstract : 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(H2 O)6 3+ water-exchange reactions. A "One-by-one" method is proposed to obtain the most representative number and arrangement of explicit H2 Os in the second hydration sphere. First, all the possible ways to locate one explicit H2 O in second sphere ( N m ′ = 1) based on the gas phase structure ( N m ′ = 0) are examined, and the optimal pathway (with the lowest energy barrier) for N m ′ = 1 is determined. Next, more explicit H2 Os are added one by one until the inner-sphere is fully hydrogen bonded. Finally, the optimal pathways with N m ′ = 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 N m ′ = 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.