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Quantum-chemical simulations of the hydration of Pb(II) ion: structure, hydration energies, and pKa1 value

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Abstract

Thermodynamic and structural aspects of the hydration of Pb(II) ions were explored based on DFT calculations combined with the supermolecular/continuum solvent model. Hydration of Pb(II) was considered as the formation of Pb(H2O)n2+ aqua complexes (n=6−9) from the gas phase Pb(II) ion. Hexa- and hepta-aqua Pb(II) complexes were shown to exhibit the hemidirected symmetry, while those containing eight and nine water molecules are characterized by the holodirected symmetry. The calculations showed that because Pb(H2O)n2+ complexes with six to nine water molecules have comparable thermodynamic stabilities, such complexes are likely to coexist in aqueous solutions. The deprotonation of Pb(H2O)n2+ complexes was shown to result in the formation of the mono-hydroxo complex [Pb(H2O)4OH]+. The pKa1 value determined for this reaction (7.58 for Pb(H2O)62+) was close to the experimental value of 7.61 used in recent models of aquatic equilibria. The density functional method ω-B97X(PCM-UAO) in combination with the atomic basis set 6-311++G(d,p) for O and H and the small-core electron effective pseudopotential (ECP) with the aug-cc-pvdz-PP basis set for Pb can be recommended for such calculations.

Structures of Pb(II) ions with varying numbers of water molecules in the inner hydration shell

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Acknowledgments

This work was supported by the Ministry of Education and Science of the Russian Federation (Project No.5382.2017).

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Authors and Affiliations

  1. Department of Inorganic Chemistry, Kazan National Research Technological University, K. Marx Street 68, Kazan, Russian Federation, 420015

    Andrey M. Kuznetsov & Alexey N. Masliy

  2. Department of Civil and Environmental Engineering, University of Washington, Box 352700, Seattle, WA, 98195-2700, USA

    Gregory V. Korshin

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  1. Andrey M. Kuznetsov
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  2. Alexey N. Masliy
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Correspondence to Gregory V. Korshin.

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Supplementary data associated with this article (four tables presenting Cartesian coordinates of Pb(II) complexes modeled in this study, hydration energies of Pb(II) ion and the averaged Pb-O distances in hexa-aqua complex calculated using the all-electron basis set for Pb, Gibbs free energy and pKa1 value for the hydrolysis of Pb(II) ion determined for different initial composition of the aqua complexes) can be found in the online version of this paper. (DOCX 27 kb)

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Kuznetsov, A.M., Masliy, A.N. & Korshin, G.V. Quantum-chemical simulations of the hydration of Pb(II) ion: structure, hydration energies, and pKa1 value. J Mol Model 24, 193 (2018). https://doi.org/10.1007/s00894-018-3726-4

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