Applicability of the Generalized Stokes-Einstein Equation of Mode-Coupling Theory to Near-Critical Polyelectrolyte...

We examine whether the mode-coupling theory of Kawasaki and Ferrell (KF) [Kawasaki, K. Kinetic Equations and Time Correlation Functions of Critical Fluctuations. Ann. Phys. 1970, 61 (1), 1-56; Ferrell, R. A. Decoupled-Mode Dynamical Scaling Theory of the Binary-Liquid Phase Transition. Phys. Rev. Lett. 1970, 24 (21), 1169-1172] can describe dynamic light scattering (DLS) measurements of the dynamic structure factor of near-critical polyelectrolyte complex (PC) solutions that have been previously shown to exhibit a theoretically unanticipated lower critical solution temperature type phase behavior, i.e., phase separation upon heating, and a conventional pattern of static critical properties (low angle scattering intensity and static correlation, ξ_s) as a function of reduced temperature. Good qualitative accord is observed between our DLS measurements and the KF theory. In particular, we observe that the collective diffusion coefficient D_c of the PC solutions obeys the generalized Stokes-Einstein equation (GSE), D_c = k_BT/6πηξ_s, where ξ_s is specified from our previous measurements and where η is measured by capillary rheometry under the same thermodynamic conditions as in our previous study of these solutions, allowing for a no-free-parameter test of the GSE. We also find that even the wavevector (q)-dependent collective diffusion coefficient D_c(q), measured by varying the scattering angle in the DLS measurements over a large range, is also well-described by the mean-field version of the KF theory. We find it remarkable that the KF theory provides such a robust description of collective diffusion in these complex charged polyelectrolyte blends under near-critical conditions given that charge fluctuations and association of the polymers might be expected to lead to physical complications that would invalidate the standard model of uncharged fluid mixtures.