Hydrodynamic density functional theory for mixtures from a variational principle and its application to droplet coalescence.

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Dynamic density functional theory (DDFT) allows the description of microscopic dynamical processes on the molecular scale extending classical DFT to non-equilibrium situations. Since DDFT and DFT use the same Helmholtz energy functionals, both predict the same density profiles in thermodynamic equilibrium. We propose a molecular DDFT model, in this work also referred to as hydrodynamic DFT, for mixtures based on a variational principle that accounts for viscous forces as well as diffusive molecular transport via the generalized Maxwell-Stefan diffusion. Our work identifies a suitable expression for driving forces for molecular diffusion of inhomogeneous systems. These driving forces contain a contribution due to the interfacial tension. The hydrodynamic DFT model simplifies to the isothermal multicomponent Navier-Stokes equation in continuum situations when Helmholtz energies can be used instead of Helmholtz energy functionals, closing the gap between micro- and macroscopic scales. We show that the hydrodynamic DFT model, although not formulated in conservative form, globally satisfies the first and second law of thermodynamics. Shear viscosities and Maxwell-Stefan diffusion coefficients are predicted using an entropy scaling approach. As an example, we apply the hydrodynamic DFT model with a Helmholtz energy density functional based on the perturbed-chain statistical associating fluid theory equation of state to droplet and bubble coalescence in one dimension and analyze the influence of additional components on coalescence phenomena.