Structure and dynamics of concentrated hydrochloric acid solutions.

Self-consistent iterative multistate empirical valence bond (SCI-MS-EVB) simulations for four different concentrated hydrochloric acid (HCl) concentrations (0.43, 0.85, 1.68, and 3.26 M) were conducted to study the structure and dynamic properties of the aqueous multiple excess proton systems. The present, more extensive simulations, confirm that the hydrated excess protons have a tendency to form metastable contact ion pairs by positioning the hydronium oxygen lone pair sides toward one another, in agreement with earlier work [ Wang, F. Izvekov, S. Voth, G. A. J. Am. Chem. Soc. 2008 , 130 , 3120 ]. This unusual behavior results from the special "amphiphilic" nature of the hydrated excess proton. Increasing the acid concentration to 3.26 M was found to have minor effects on the solvation structures of the hydrated proton and chloride counterion, while the average lifetime of the hydrated proton contact ion pairs was reduced. The addition of salts (KCl and NaCl) into the acid solution increases the stability of the hydrated proton pairs and reduces the proton diffusion.