Rational Design of Nonbonded Point Charge Models for Highly Charged Metal Cations with Lennard-Jones 12-6 Potential

Abstract

Here, we developed nonbonded point charge models using a simple Lennard-Jones (LJ) 12-6 potential for highly charged metal cations (18 trivalent and 6 tetravalent ions) for use with 11 water models of TIP3P, OPC3, SPC/E, SPC/Eb, TIP3P-FB, a99SB-disp, TIP4P-Ew, OPC, TIP4P/2005, TIP4P-D, and TIP4P-FB. The designed models simultaneously reproduce the hydration free energy (HFE) and ion-oxygen distance (IOD) in the first hydration shell with an error within 1 kcal/mol and 0.01 Å on average, respectively, and yield reasonable coordination numbers for most cations. Such performance is equivalent to the previously reported point charge models using a more complex 12-6-4 LJ-type potential, while the LJ R parameters of our models are much close to Shannon s revised effective ion radii than that of the 12-6-4 models. Our designed models overestimate the diffusion constants of several trivalent ions by 5-68%. The performance in predicting osmotic coefficients of trivalent chlorides in aqueous solution depends on the salt type. A calibration of cation-anion interacting LJ parameters reproduces the experimental osmotic coefficients of an AlCl3 solution at 0.2-3.0 mol/L. The effectiveness of our new models is further demonstrated by simulating a metalloprotein system with four force field/water combinations. This work facilitates accurate modeling of metal-containing systems by a variety of force fields and water models in aqueous solution.