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Among different thermodynamic properties of liquids, the entropy is one of the hardest quantities to estimate. Therefore, the development of models allowing accurate estimations of the entropy for different mechanisms of interatomic interactions represents an important problem. Here, we propose a method for estimating the excess entropy of simple liquids not too far from the liquid–solid phase transition. The method represents a variant of cell theory, which particularly emphasizes relations between liquid state thermodynamics and collective modes properties. The method is applied to calculate the excess entropy of inverse-power-law fluids with ∝r−n repulsive interactions. The covered range of potential softness is extremely wide, including the very soft Coulomb (n = 1) case, much steeper n = 6 and n = 12 cases, and the opposite hard-sphere interaction limit (n = ∞). An overall reasonably good agreement between the method's outcome and existing "exact" results is documented at sufficiently high fluid densities. Its applicability condition can be conveniently formulated in terms of the excess entropy itself. The method is also applied to the Lennard-Jones potential but demonstrates considerably lower accuracy in this case. Our results should be relevant to a broad range of liquid systems that can be described with isotropic repulsive interactions, including liquid metals, macromolecular systems, globular proteins, and colloidal suspensions. [ABSTRACT FROM AUTHOR]

Tunable interactions in colloids, induced by rotating electric or magnetic fields, provide a flexible and promising tool for self-assembly of soft materials, as well as for fundamental particle-resolved studies of phase transitions and other generic phenomena in condensed matter. In the case of two-dimensional systems and the in-plane rotating fields, the interactions are known to have a long-range (dipolar) attraction and an expressed three-body part at short distances, but still remain poorly understood. Here, we show that the interactions and polarization mechanisms governing the tunable interactions can be described, calculated, and analyzed in detail with the diagrammatic method we proposed. The diagrams yield a clear illustration of different polarization processes contributing to the Keesom, Debye, London, self, and external energies, classified in colloids similarly to intermolecular interactions. The real tunable interactions, obtained with the boundary element method, can be simply and accurately interpolated with the set of basis of the diagrams attributed to different physically clear polarization processes. Calculation of large-distance behavior and interpolation of the many-body interactions (and analysis of the leading mechanisms contributing to them) excellently illustrate that the diagrammatic method provides deep insights into the nature of tunable interactions. The method can be generalized for multicomponent systems, suspensions of particles with a composite structure and a complicated shape. The results provide significant advance in theoretical methods for detailed analysis of tunable interactions in colloids and, therefore, the method is of broad interest in condensed matter, chemical physics, physical chemistry, materials science, and soft matter. [ABSTRACT FROM AUTHOR]

Accurate analysis of pair correlations in condensed matter allows us to establish relations between structures and thermodynamic properties and, thus, is of high importance for a wide range of systems, from solids to colloidal suspensions. Recently, the interpolation method (IM) that describes satisfactorily the shape of pair correlation peaks at short and at long distances has been elaborated theoretically and using molecular dynamics simulations, but it has not been verified experimentally as yet. Here, we test the IM by particle-resolved studies with colloidal suspensions and with complex (dusty) plasmas and demonstrate that, owing to its high accuracy, the IM can be used to experimentally measure parameters that describe interaction between particles in these systems. We used three- and two-dimensional colloidal crystals and monolayer complex (dusty) plasma crystals to explore suitability of the IM in systems with soft to hard-sphere-like repulsion between particles. In addition to the systems with pairwise interactions, if many-body interactions can be mapped to the pairwise ones with some effective (e.g., density-dependent) parameters, the IM could be used to obtain these parameters. The results reliably show that the IM can be effectively used for analysis of pair correlations and interactions in a wide variety of systems and therefore is of broad interest in condensed matter, complex plasma, chemical physics, physical chemistry, materials science, and soft matter. [ABSTRACT FROM AUTHOR]

We study the phase diagram of a two-dimensional (2D) system of colloidal particles, interacting via an isotropic potential with a short-ranged Yukawa repulsion and a long-ranged dipolar attraction. Such interactions in 2D colloidal suspensions can be induced by rapidly rotating in-plane magnetic (or electric) fields. Using computer simulations and liquid integral equation theory, we calculate the bulk phase diagram, which contains gas, crystalline, liquid, and supercritical fluid phases. The densities at the critical and triple points in the phase diagram are governed by the softness of Yukawa repulsion and can therefore be largely tuned. We observe that the liquid-gas binodals exhibit universal behavior when the effective temperature (given by the inverse magnitude of the dipolar attractions) is normalized by its value at the critical point and the density is normalized by the squared Barker-Henderson diameter. The results can be verified in particle-resolved experiments with colloidal suspensions. [ABSTRACT FROM AUTHOR]

Newton's third law--the action-reaction symmetry--can be violated for effective interbody forces in open and nonequilibrium systems that are ubiquitous in areas as diverse as complex plasmas, colloidal suspensions, active and living soft matter, and social behavior. While studying monolayer complex plasma (confined charged particles in an ionized gas) with nonreciprocal interactions mediated by plasma flows, in silico we found that an interplay between melting and thermal activation drastically transforms the collective dynamics: the order-disorder transition modifies the system's thermal steady state so that the crystal tends to melt, whereas the fluid tends to freeze, jumping chaotically between the two states. We identified this collective chaotic behavior as strange attractors formed in a monolayer complex plasma and link the strange attractor behavior to the specifics of interparticle interactions. [ABSTRACT FROM AUTHOR]