화학공학소재연구정보센터
Journal of Physical Chemistry, Vol.99, No.33, 12647-12654, 1995
Ionic Association of Na+-Cl-, Na+-Na+, and Cl--Cl- in Methanol - Mean Force Potentials and Friction Kernels
Solvent-averaged potentials for Na+-Cl-, Na+-Na+, and Cl--Cl- in methanol have been evaluated using the constrained molecular dynamics simulation technique. Solvent contributions to the total force on the solute pairs have been analyzed carefully in all of the systems. In order to get a deeper insight into the influence of the solvent on the ion pairs, the most probable solvent distributions at the relevant points of the calculated mean force potentials have been studied. Our mean force potentials show important discrepancies with the ones obtained using the RISM (reference interaction site model) approximation. Friction kernels for the relative dynamics of the ion pairs have also been evaluated. The passage across the barrier existing in the Na+-Cl- mean-force potential has been analyzed in light of Kramers and Grote-Hynes theories. It turns out that the association-dissociation process takes place in the polarization caging regime. A comparison between our results and the ones corresponding to the same ion pairs in water has been done.