Faculté des sciences

Dynamics of localized particles from density functional theory

Reinhardt, Johannes ; Brader, Joseph M.

In: Physical Review E - Statistical, nonlinear, and soft matter physics, 2012, vol. 85, no. 1, p. 011404

A fundamental assumption of the dynamical density functional theory (DDFT) of colloidal systems is that a grand-canonical free-energy functional may be employed to generate the thermodynamic driving forces. Using one-dimensional hard rods as a model system, we analyze the validity of this key assumption and show that unphysical self-interactions of the tagged particle density fields, arising from... Plus

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    Summary
    A fundamental assumption of the dynamical density functional theory (DDFT) of colloidal systems is that a grand-canonical free-energy functional may be employed to generate the thermodynamic driving forces. Using one-dimensional hard rods as a model system, we analyze the validity of this key assumption and show that unphysical self-interactions of the tagged particle density fields, arising from coupling to a particle reservoir, are responsible for the excessively fast relaxation predicted by the theory. Moreover, our findings suggest that even employing a canonical functional would not lead to an improvement for many-particle systems, if only the total density is considered. We present several possible schemes to suppress these effects by incorporating tagged densities. When applied to confined systems, we demonstrate, using a simple example, that DDFT necessarily leads to delocalized tagged particle density distributions, which do not respect the fundamental geometrical constraints apparent in Brownian dynamics simulation data. The implication of these results for possible applications of DDFT to treat the glass transition are discussed.