Oleg Vasilyev

Monte Carlo simulation results for critical Casimir forces

The confinement of critical fluctuations in soft media induces critical Casimir forces acting on the confining surfaces. The temperature and geometry dependences of such forces are characterized by universal scaling functions. A novel approach is presented to determine them for films via Monte Carlo simulations of lattice models. The method is based on an integration scheme of free energy differences. Our results for the Ising and the XY universality class agree well with corresponding experimental results for wetting layers of classical binary liquid mixtures and of 4He, respectively.

Universal scaling functions of critical Casimir forces obtained by Monte Carlo simulations

Effective Casimir forces induced by thermal fluctuations in the vicinity of bulk critical points are studied by means of Monte Carlo simulations in three-dimensional systems for film geometries and within the experimentally relevant Ising and XY universality classes. Several surface universality classes of the confining surfaces are considered, some of which are relevant for recent experiments. An approach introduced previously [O. Vasilyev, EPL 80, 60009 (2007)], based inter alia on an integration scheme of free-energy differences, is utilized to compute the universal scaling functions of the critical Casimir forces in the critical range of temperatures above and below the bulk critical temperature. The resulting predictions are compared with corresponding experimental data for wetting films of fluids and with available theoretical results.

Precursors of order in aggregates of patchy particles

We study computationally the local structure of aggregated systems of patchy particles. By calculating the probability distribution functions of various rotational invariants we can identify the precursors of orientation order in amorphous phase. Surprisingly, the strongest signature of local order is observed for four-patch particles with tetrahedral symmetry, not for six-patch particles with the cubic one. This trend is exactly opposite to their known ability to crystallize. We relate this anomaly to the observation that a generic aggregate of patchy systems has a coordination number close to 4. Our results also suggest a significant correlation between rotational order in the studied liquids with the corresponding crystalline phases, making this approach potentially useful for a broader range of patchy systems.

Critical Casimir forces for Ising films with variable boundary fields

Monte Carlo simulations based on an integration scheme for free energy differences is used to compute critical Casimir forces for three-dimensional Ising films with various boundary fields. We study the scaling behavior of the critical Casimir force, including the scaling variable related to the boundary fields. Finite size corrections to scaling are taken into account. We pay special attention to that range of surface field strengths within which the force changes from repulsive to attractive upon increasing the temperature. Our data are compared with other results available in the literature.

Critical Casimir interactions between spherical particles in the presence of bulk ordering fields

The spatial suppression of order parameter fluctuations in a critical media produces critical Casimir forces acting on confining surfaces. This scenario is realized in a critical binary mixture near the demixing transition point that corresponds to the second-order phase transition of the Ising universality class. Due to these critical interactions similar colloids, immersed in a critical binary mixture near the consolute point, exhibit attraction. The numerical method for computation of the interaction potential between two spherical particles using Monte Carlo simulations for the Ising model is proposed. This method is based on the integration of the local magnetization over the applied local magnetic field. For the stronger interaction the concentration of the component of the mixture that does not wet colloidal particles should be larger than the critical concentration. The strongest amplitude of the interactions is observed below the critical point.

Critical Casimir forces for films with bulk ordering fields

The confinement of long-ranged critical fluctuations in the vicinity of second-order phase transitions in fluids generates critical Casimir forces acting on confining surfaces or among particles immersed in a critical solvent. This is realized in binary liquid mixtures close to their consolute point Tc which belong to the universality class of the Ising model. The deviation of the difference of the chemical potentials of the two species of the mixture from its value at criticality corresponds to the bulk magnetic filed of the Ising model. By using Monte Carlo simulations for this latter representative of the corresponding universality class we compute the critical Casimir force as a function of the bulk ordering field at the critical temperature . We use a coupling parameter scheme for the computation of the underlying free energy differences and an energy-magnetization integration method for computing the bulk free energy density which is a necessary ingredient. By taking into account finite-size corrections, for various types of boundary conditions we determine the universal Casimir force scaling function as a function of the scaling variable associated with the bulk field. Our numerical data are compared with analytic results obtained from mean-field theory.

Two-temperature Langevin dynamics in a parabolic potential.

We study a planar two-temperature diffusion of a Brownian particle in a parabolic potential. The diffusion process is defined in terms of two Langevin equations with two different effective temperatures in the X and the Y directions. In the stationary regime the system is described by a nontrivial particle position distribution, P(x,y), which we determine explicitly. We show that this distribution corresponds to a nonequilibrium stationary state, characterized by the presence of space-dependent particle currents which exhibit a nonzero rotor. Theoretical results are confirmed by the numerical simulations.

Interfaces in driven Ising models: shear enhances confinement

We use a phase-separated driven two-dimensional Ising lattice gas to study fluid interfaces exposed to shear flow parallel to the interface. The interface is stabilized by two parallel walls with opposing surface fields, and a driving field parallel to the walls is applied which (i) either acts locally at the walls or (ii) varies linearly with distance across the strip. Using computer simulations with Kawasaki dynamics, we find that the system reaches a steady state in which the magnetization profile is the same as that in equilibrium, but with a rescaled length implying a reduction of the interfacial width. An analogous effect was recently observed in sheared phase-separated colloidal dispersions. Pair correlation functions along the interface decay more rapidly with distance under drive than in equilibrium and for cases of weak drive, can be rescaled to the equilibrium result.

Critical adsorption and critical Casimir forces in the canonical ensemble

Critical properties of a liquid film between two planar walls are investigated in the canonical ensemble, within which the total number of fluid particles, rather than their chemical potential, is kept constant. The effect of this constraint is analyzed within mean-field theory (MFT) based on a Ginzburg-Landau free-energy functional as well as via Monte Carlo simulations of the three-dimensional Ising model with fixed total magnetization. Within MFT and for finite adsorption strengths at the walls, the thermodynamic properties of the film in the canonical ensemble can be mapped exactly onto a grand canonical ensemble in which the corresponding chemical potential plays the role of the Lagrange multiplier associated with the constraint. However, due to a nonintegrable divergence of the mean-field order parameter profile near a wall, the limit of infinitely strong adsorption turns out to be not well-defined within MFT, because it would necessarily violate the constraint. The critical Casimir force (CCF) acting on the two planar walls of the film is generally found to behave differently in the canonical and grand canonical ensembles. For instance, the canonical CCF in the presence of equal preferential adsorption at the two walls is found to have the opposite sign and a slower decay behavior as a function of the film thickness compared to its grand canonical counterpart. We derive the stress tensor in the canonical ensemble and find that it has the same expression as in the grand canonical case, but with the chemical potential playing the role of the Lagrange multiplier associated with the constraint. The different behavior of the CCF in the two ensembles is rationalized within MFT by showing that, for a prescribed value of the thermodynamic control parameter of the film, i.e., density or chemical potential, the film pressures are identical in the two ensembles, while the corresponding bulk pressures are not.

Critical Casimir forces in the presence of random surface fields

We study critical Casimir forces (CCFs) fC for films of thickness L which in the three-dimensional bulk belong to the Ising universality class and which are exposed to random surface fields (RSFs) on both surfaces. We consider the case in which, in the absence of RSFs, the surfaces of the film belong to the surface universality class of the so-called ordinary transition. We carry out a finite-size scaling analysis and show that for weak disorder, CCFs still exhibit scaling, acquiring a random field scaling variable w that is zero for pure systems. We confirm these analytic predictions by Monte Carlo (MC) simulations. Moreover, our MC data show that fC varies as fC(w→0)-fC(w=0)∼w2. Asymptotically, for large L, w scales as w∼L-0.26→0, indicating that this type of disorder is an irrelevant perturbation of the ordinary surface universality class. However, for thin films such that w≃1, we find that the presence of RSFs with vanishing mean value increases significantly the strength of CCFs, as compared to systems without them, and it shifts the extremum of the scaling function of fC toward lower temperatures. But fC remains attractive.