Journal of Chemical Physics, Vol.109, No.5, 1930-1938, 1998
Static structure of electrolyte systems and the linear response function on the basis of a dressed-ion theory
The static structure of a bulk electrolyte solution or colloid system is investigated in the framework of a dressed-ion theory (DIT). The number-number, charge-number, and charge-charge static structure factors are calculated and are seen to depend only on the linear response function of the DIT <(alpha)over cap>(k), the alpha function therefore determining the charge structure of the fluid in what is an expression of the fluctuation-dissipation theorem. The expression of the static structure factors for one-component charged spheres (OCCS) is evaluated in the random-phase approximation and in a modified version of the mean-spherical approximation (MSA), using the hard-sphere fluid as a reference system, and an explicit expression for the linear response function and dielectric function is obtained. The effective screening length (kappa(-1)) and the transition from monotonic exponential to oscillatory behavior obtained from the modified MSA expression of the alpha function are seen to improve the ones derived from the second moment condition at intermediate concentrations. The internal charge density distribution of a dressed ion and the renormalized ion charges (q*) are also investigated. The oscillatory behavior of the charge distributions suggests an "onionlike model," with the central ion surrounded by spherical charge shells. The effective charges calculated from the modified MSA are seen to diverge in the neighborhood of the transition from the monotonic exponential regime to the oscillatory regime. In the Limit of vanishing concentration, Debye-Huckel (DH) results are recovered.