The charge-dipole contribution to the density-density correlation matrix in near-critical electrolytes

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Abstract A charge-dipole term in the ion-solvent contribution to the density-density correlation matrix of an ionic solution is identified, and its effect on the thermodynamics of the solution near its critical point is investigated. It is pointed out that such a term will appear in the description of an ionic melt in the absence of a molecular solvent if the melt is regarded as a mixture of free ions in a solvent of ions that have ionically associated to some extent into dipolar pairs. It is concluded that the presence of such a charge-dipole term might significantly perturb the Ising-like thermodynamic behavior that one expects in a pure dipolar solvent in its critical region, but in a way that is too system-dependent to permit universal statements to be made about its quantitative effect.