An Ab Initio Study of Aqueous Copper(I) Speciation in the Presence of Chloride

The determination of multiple energy minima on complex potential energy surfaces is challenging. A systematic desymmetrization procedure was employed to find stationary points on the copper(I) + chloride + water potential energy surface using HF, MP2, and B3LYP methods in conjunction with the 6-31G*...

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Bibliographic Details
Main Authors: Daniel C. M. Whynot, Christopher R. Corbeil, Darren J. W. Mercer, Cory C. Pye
Format: Article
Language:English
Published: MDPI AG 2025-07-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/15/3147
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Summary:The determination of multiple energy minima on complex potential energy surfaces is challenging. A systematic desymmetrization procedure was employed to find stationary points on the copper(I) + chloride + water potential energy surface using HF, MP2, and B3LYP methods in conjunction with the 6-31G*, 6-31+G*, and 6-311+G* basis sets. Comparison with experimental results demonstrated that the speciation of copper(I) in the presence of chloride and water may be formulated as [CuCl(H<sub>2</sub>O)]<sup>0</sup>, [CuCl<sub>2</sub>]<sup>−</sup>, and [CuCl<sub>3</sub>]<sup>2−</sup>. Our results indicate that the combination of the MP2 method along with basis sets containing diffuse functions gives excellent agreement with experimental Cu-Cl distances and vibrational frequencies. Poorer results were obtained at the HF levels and/or using the 6-31G* basis set.
ISSN:1420-3049