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The existence of the dielectric constant e is investigated for fluid mixtures of rigid polar molecules. The investigation is performed using the functional‐derivative formalism for mixtures, and is closely analogous to that previously carried out for pure dipolar fluids [J. Chem. Phys. 68, 5199 (1978)]. Sufficient conditions for the existence of e are obtained in terms of the direct correlation function matrix cαβ(12). It is found that e exists if cαβ(12) depends only on relative positions and orientations, and becomes asymptotic to −ϑαβ(12)/kT at long range, where ϑαβ(12) is the dipole–dipole potential between a molecule of species α and one of species β. An expression for e in terms of the short‐range total correlation function matrix emerges automatically from the development. This expression is equivalent to an earlier result obtained by a different method. Expressions for e in terms of cαβ(12) are derived for axially symmetric molecules and for molecules of arbitrary symmetry. In the former case, the...

Existence of the dielectric constant in dipolar fluid mixtures