Ion-specific thermodynamics of multicomponent electrolytes: a hybrid HNC/MD approach.
Using effective infinite dilution ion-ion interaction potentials derived from explicit-water molecular dynamics (MD) computer simulations in the hypernetted-chain (HNC) integral equation theory we calculate the liquid structure and thermodynamic properties, namely, the activity and osmotic coefficients of various multicomponent aqueous electrolyte mixtures. The electrolyte structure expressed by the ion-ion radial distribution functions is for most ions in excellent agreement with MD and implicit solvent Monte Carlo (MC) simulation results. Calculated thermodynamic properties are also represented consistently among these three methods. Our versatile HNC/MD hybrid method allows for a quick prediction of the thermodynamics of multicomponent electrolyte solutions for a wide range of concentrations and an efficient assessment of the validity of the employed MD force-fields with possible implications in the development of thermodynamically consistent parameter sets.
Vrbka
Lubos
L
Institut für Physikalische und Theoretische Chemie, Universität Regensburg, 93040 Regensburg, Germany. lubos@vrbka.net
Lund
Mikael
M
Kalcher
Immanuel
I
Dzubiella
Joachim
J
Netz
Roland R
RR
Kunz
Werner
W
D004573:Electrolytes / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D009010:Monte Carlo Method; D013816:Thermodynamics
D004573:Electrolytes