Failure of standard density functional theory to describe the phase behavior of a fluid of hard right isosceles triangles

A fluid of hard right isosceles triangles was studied using an extension of scaled-particle density-functional theory which includes the exact third virial coefficient. We show that the only orientationally ordered stable liquid-crystal phase predicted by the theory is the uniaxial nematic phase, in agreement with the second-order virial theory. By contrast, Monte Carlo simulations predict exotic liquid-crystal phases exhibiting tetratic and octatic correlations, with orientational distribution functions having four and eight equivalent peaks, respectively. This demonstrates the failure of the standard density-functional theory based on two- and three-body correlations to describe high-symmetry orientational phases in two-dimensional hard right-triangle fluids, and it points to the necessity to reformulate the theory to take into account high-order body correlations and ultimately particle self-assembling and clustering effects. This avenue may represent a great challenge for future research, and we discuss some fundamental ideas to construct a modified version of density-functional theory to account for these clustering effects.

Failure of standard density functional theory to describe the phase behavior of a fluid of hard right isosceles triangles Articles