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

Title: An Ab Initio Study of Aqueous Copper(I) Speciation in the Presence of Chloride
Authors: Daniel C. M. Whynot; Christopher R. Corbeil; Darren J. W. Mercer; Cory C. Pye
Source: Molecules ; Volume 30 ; Issue 15 ; Pages: 3147
Publisher Information: Multidisciplinary Digital Publishing Institute
Publication Year: 2025
Collection: MDPI Open Access Publishing
Subject Terms: ab initio; density functional; copper(I) chloro complexes; structure; vibrational frequencies
Subject Geographic: agris
Description: 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(H2O)]0, [CuCl2]−, and [CuCl3]2−. 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.
Document Type: text
File Description: application/pdf
Language: English
Relation: Inorganic Chemistry; https://dx.doi.org/10.3390/molecules30153147
DOI: 10.3390/molecules30153147
Availability: https://doi.org/10.3390/molecules30153147
Rights: https://creativecommons.org/licenses/by/4.0/
Accession Number: edsbas.CEBB3BB5
Database: BASE