CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

• Published in: Geofluids 2018-01, Vol.2018 (2018), p.1-12
• Main Authors: Brugger, Joël, Migdiov, A. A., Liu, Weihua, Mei, Yuan, Williams-Jones, A. E.
• Format: Article
• Language: English
• Subjects: Bonding strength; Chemical bonds; Chloride; Coefficients; Coordination compounds; Copper; Copper chloride; Copper chloride, AIMD, hydrothermal, vapor transport; Density; Dynamics; Earth Sciences; Fluid dynamics; Fluids; Fugacity; GEOSCIENCES; Hydration; Hydrogen; Hydrogen bonding; Hydrogen bonds; Hydrothermal fluids; Metal complexes; Metals; Molecular chains; Molecular dynamics; Monte Carlo simulation; Physical chemistry; Physics; Simulation; Solubility; Studies; Uncertainty; Vapor phases; Vapors; Water; Water activity; Water vapor; Water vapour
• ISSN: 1468-8115; 1468-8123
• DOI: 10.1155/2018/4279124

We investigated the hydration of the CuCl0 complex in HCl-bearing water vapor at 350°C and a vapor-like fluid density between 0.02 and 0.09 g/cm3 using ab initio molecular dynamics (MD) simulations. The simulations reveal that one water molecule is strongly bonded to Cu(I) (first coordination shell), forming a linear [H2O-Cu-Cl]0 moiety. The second hydration shell is highly dynamic in nature, and individual configurations have short life-spans in such low-density vapors, resulting in large fluctuations in instantaneous hydration numbers over a timescale of picoseconds. The average hydration number in the second shell (m) increased from ~0.5 to ~3.5 and the calculated number of hydrogen bonds per water molecule increased from 0.09 to 0.25 when fluid density (which is correlated to water activity) increased from 0.02 to 0.09 g/cm3 (fH2O 1.72 to 2.05). These changes of hydration number are qualitatively consistent with previous solubility studies under similar conditions, although the absolute hydration numbers from MD were much lower than the values inferred by correlating experimental Cu fugacity with water fugacity. This could be due to the uncertainties in the MD simulations and uncertainty in the estimation of the fugacity coefficients for these highly nonideal “vapors” in the experiments. Our study provides the first theoretical confirmation that beyond-first-shell hydrated metal complexes play an important role in metal transport in low-density hydrothermal fluids, even if it is highly disordered and dynamic in nature.