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Molecular simulation study on K+–Cl− ion pair in geological fluids

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Abstract

This paper reports a classical molecular dynamics study of the potential of mean forces (PMFs), association constants, microstructures K+–Cl− ion pair in supercritical fluids. The constrained MD method is used to derive the PMFs of K+–Cl− ion pair from 673 to 1273 K in low-density water (0.10–0.60 g/cm3). The PMF results show that the contact ion-pair (CIP) state is the one most energetically favored for a K+–Cl− ion pair. The association constants of the K+–Cl− ion pair are calculated from the PMFs, indicating that the K+–Cl− ion pair is thermodynamically stable. It gets more stable as T increases or water density decreases. The microstructures of the K+–Cl− ion pair in the CIP and solvent-shared ion-pair states are characterized in detail. Moreover, we explore the structures and stabilities of the KCl–Au(I)/Cu(I) complexes by using quantum mechanical calculations. The results reveal that these complexes can remain stable for T up to 1273 K, which indicates that KCl may act as a ligand complexing ore-forming metals in hydrothermal fluids.

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Acknowledgments

We acknowledge National Science Foundation of China (Nos. 41222015, 41273074, 41425009, and 41572027), Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase), the Foundation for the Author of National Excellent Doctoral Dissertation of P. R. China (No. 201228), Newton International Fellowship Program and the financial support from the State Key Laboratory at Nanjing University. We are grateful to the High Performance Computing Center of Nanjing University for allowing us to use the IBM Blade cluster system.

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Authors and Affiliations

  1. State Key Laboratory for Mineral Deposits Research, School of Earth Sciences and Engineering, Nanjing University, Nanjing, 210046, People’s Republic of China

    Mengjia He, Xiandong Liu, Xiancai Lu & Rucheng Wang

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  1. Mengjia He
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  2. Xiandong Liu
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  3. Xiancai Lu
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  4. Rucheng Wang
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Correspondence to Xiandong Liu.

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He, M., Liu, X., Lu, X. et al. Molecular simulation study on K+–Cl− ion pair in geological fluids. Acta Geochim 36, 1–8 (2017). https://doi.org/10.1007/s11631-016-0130-6

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  • DOI: https://doi.org/10.1007/s11631-016-0130-6

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