Journal of Molecular Modeling

, 25:291 | Cite as

Interaction of H2O with (CuS)n, (Cu2S)n, and (ZnS)n small clusters (n = 1–4, 6): relation to the aggregation characteristics of metal sulfides at aqueous solutions

  • Kerry Wrighton-Araneda
  • René Ruby-Figueroa
  • Humberto Estay
  • Diego Cortés-ArriagadaEmail author
Original Paper
Part of the following topical collections:
  1. QUITEL 2018 (44th Congress of Theoretical Chemists of Latin Expression)


The interaction of H2O onto small CuS, Cu2S, and ZnS clusters was theoretically studied by Density Functional Theory computations to get insights into the aggregation characteristics of metal sulfides at aqueous solutions. The results show the charge-controlled interactions with polarized solvent molecules are favored on the ZnS clusters compared with CuS and Cu2S clusters. Moreover, the chemical adsorption of H2O molecules is energetically favored onto ZnS clusters with higher interaction energies of up to 35.4 kcal/mol compared with CuS and Cu2S clusters (up to 31.3 kcal/mol), where the stability of H2O adsorption decreases as the size of the clusters increases. However, thermochemical analysis shows that the adsorption of H2O on copper sulfides is not a spontaneous process at room temperature. Additionally, the electrostatic energy of H2O onto the Cu2S and CuS clusters is lower than that associated with the H2O–H2O interactions, suggesting that copper precipitates prefer to bind between them at early stages of the precipitation process due to an unfavorable solvent-solute interaction. Dispersion forces play a relative key role in the interaction of water on copper sulfides, while for zinc sulfide clusters, the adsorption energy is slightly influenced by dispersion contributions. Accordingly, the aggregation of zinc sulfides in a water environment is expected to be lower compared with copper sulfides, and where the aggregation characteristics are not determined by the binding energy of the sulfides, but of the ability to interact with the solvent molecules. These statements were confirmed by experimental optical microscopy analysis and settling tests during precipitation processes in water. Therefore, this work allows proposing a simple strategy to study the aggregation characteristics of metal sulfides, which turns useful for use in hydrometallurgical applications.


DFT calculations Metal sulfide precipitates Hydrometallurgy Clusters 



D.C-A acknowledges the computational resources through the CONICYT/FONDEQUIP project EQM180180. H.E and RRF acknowledge the FONDEF/IDeA Program, FONDEF/CONICYT 2017+ID17I10021. Powered@NLHPC: This research was partially supported by the supercomputing infrastructure of NLHPC (ECM-02).

Funding information

This work received financial support from the CONICYT/FONDECYT 11170289.

Compliance with ethical standards

Conflict of interest

The authors declare that there are no competing interests.

Supplementary material

894_2019_4161_MOESM1_ESM.docx (73 kb)
ESM 1 (DOCX 72 kb)


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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Programa Institucional de Fomento a la Investigación, Desarrollo e InnovaciónUniversidad Tecnológica MetropolitanaSan JoaquínChile
  2. 2.Advanced Mining Technology Center (AMTC)University of ChileSantiagoChile

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