Combined density functional and Brazovskii theories for systems with spontaneous inhomogeneities

TL;DR

This paper develops a new density functional theory incorporating mesoscopic fluctuations via Brazovskii field theory to better predict phase diagrams of self-assembling systems, especially at high temperatures, aligning more closely with simulations.

Contribution

A novel DFT framework that explicitly includes fluctuation effects using Brazovskii theory, improving high-temperature phase diagram predictions for systems with spontaneous inhomogeneities.

Findings

Good agreement with simulations for high-T phase diagram range

Ordered phases are stable at lower T than in simulations

Equation of state and compressibility are derived

Abstract

The low-T part of the phase diagram in self-assembling systems is correctly predicted by the known versions of the density functional theory (DFT). The high-T part obtained in DFT, however, does not agree with simulations even on the qualitative level. In this work a new version of the DFT is developed. The contribution to the grand thermodynamic potential associated with mesoscopic fluctuations is explicitly taken into account. The expression for this contribution is obtained by the methods known from the Brazovskii field theory. Apart from developing the approximate expression for the grand thermodynamic potential that contains the fluctuation contribution and is ready for numerical minimization, we develop a simplified version of the theory valid for weakly ordered phases, i.e. for the high -T part of the phase diagram. The simplified theory is verified by a comparison with the results of simulations for a particular version of the short-range attraction long-range repulsion (SALR) interaction potential. Except from the fact that in our theory the ordered phases are stable at lower T than in simulations, a good agreement for the high-T part of the phase diagram is obtained for the range of density that was considered in simulations. In addition, the equation of state and compressibility isotherms are presented. Finally, the physical interpretation of the fluctuation-contribution to the grand potential is discussed in detail.