Extended dynamical density functional theory for colloidal mixtures with temperature gradients

Abstract

In the past decade, classical dynamical density functional theory (DDFT) has been developed and widely applied to the Brownian dynamics of interacting colloidal particles. One of the possible derivation routes of DDFT from the microscopic dynamics is via the Mori-Zwanzig-Forster projection operator technique with slowly varying variables such as the one-particle density. Here, we use the projection operator approach to extend DDFT into various directions: first, we generalize DDFT toward mixtures of n different species of spherical colloidal particles. We show that there are in general nontrivial cross-coupling terms between the concentration fields and specify them explicitly for colloidal mixtures with pairwise hydrodynamic interactions. Second, we treat the internal energy density as an additional slow variable and derive formal expressions for an extended DDFT containing also the internal energy density. The latter approach can in principle be applied to colloidal dynamics in a nonzero temperature gradient. For the case without hydrodynamic interactions the diffusion tensor is diagonal, while thermodiffusion--the dissipative cross-coupling term between internal energy density and concentration--is nonzero in this limit. With finite hydrodynamic interactions also cross-diffusion coefficients assume a finite value. We demonstrate that our results for the extended DDFT contain the transport coefficients in the hydrodynamic limit (long wavelengths, low frequencies) as a special case.