Molecular dynamics study of perchloric acid using the extended Madrid-2019 force field

Abstract

Perchloric acid (HClO${}_4$) is widely used to prepare perchlorate salts with applications in propellants, industry, environmental chemistry, and biology. In this work, we used the intermolecular parameters from the extended Madrid-2019 force field for the perchlorate anion (ClO${}_4^{-}$) and the oxonium cation (H${}_3$O${}^{+}$) together with TIP4P/2005 water to model perchloric acid solutions. The force field uses scaled charges of $\pm 0.85e$ for monovalent ions and has been widely applied for aqueous ionic systems. We used the model to predict thermodynamic properties [densities and temperatures of maximum in density (TMD)], structural features (ion-water correlations: ion-hydrogen and ion-oxygen), and transport properties (self-diffusion coefficients and viscosity) of perchloric acid solutions at several concentrations. Experimental densities are predicted in excellent agreement up to 10 $m$. We also performed molecular simulations over a wide range of temperatures in order to determine the TMD of perchloric acid at different molalities. Predicted viscosities at 298.15 K and 1 bar are in good agreement with experimental data for concentrations below 4 $m$. Results are discussed in terms of model strengths and limitations.

14 pages, 5 figures

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