Molecular Force Field Development for Aqueous Electrolytes: 1. Incorporating Appropriate Experimental Data and the Inadequacy of Simple Electrolyte Force Fields Based on Lennard-Jones and Point Charge Interactions with Lorentz-Berthelot Rules

作者：Moucka Filip; Nezbeda Ivo; Smith William R^*

来源：Journal of Chemical Theory and Computation, 2013, 9(11): 5076-5085.

DOI：10.1021/ct4006008

It is known that none of the available simple molecular interaction models of aqueous electrolytes based on SPC/E water and their associated force fields are able to reproduce the concentration dependence of important thermodynamic properties of even the simplest electrolyte, NaCl, at ambient conditions over the entire experimentally accessible concentration range [Moucka, F.; Nezbeda, I.; Smith, W. R. J. Chem. Phys. 2013, 138, 154102]. This paper explores the possibility of improving their performance by incorporating concentration-dependent experimental data for the total ionic chemical potential and the density into the fitting procedure, in addition to experimental values of solubility and solid chemical potential. We describe a general parameter estimation methodology for a studied class of models that incorporates the aforementioned experimental data. When the entire concentration range is considered, although the resulting force field is a slight improvement over others currently available in the literature, overall quantitative agreement with the experimental data over this range remains unsatisfactory. This indicates an inherent limitation of such simple molecular interaction models and strongly suggests that more complex mathematical forms of such models are required to quantitatively predict the properties of aqueous electrolyte solutions when the entire concentration range is of interest. Our parameter estimation methodology is also applicable to such cases.

• 出版日期2013-11