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Spatial confinement of a near-critical medium changes its fluctuation spectrum and modifies the corresponding order parameter distribution. These effects result in effective, so-called critical Casimir forces (CCFs) acting on the confining surfaces. These forces are attractive for like boundary conditions of the order parameter at the opposing surfaces of the confinement. For colloidal particles dissolved in a binary liquid mixture acting as a solvent close to its critical point of demixing, one thus expects the emergence of phase segregation into equilibrium colloidal liquid and gas phases. We analyze how such phenomena occur asymmetrically in the whole thermodynamic neighborhood of the consolute point of the binary solvent. By applying field-theoretical methods within mean-field approximation and the semi-empirical de Gennes-Fisher functional, we study the CCFs acting between planar parallel walls as well as between two spherical colloids and their dependence on temperature and on the composition of the near-critical binary mixture. We find that for compositions slightly poor in the molecules preferentially adsorbed at the surfaces, the CCFs are significantly stronger than at the critical composition, thus leading to pronounced colloidal segregation. The segregation phase diagram of the colloid solution following from the calculated effective pair potential between the colloids agrees surprisingly well with experiments and simulations.

Having smaller energy density than batteries, supercapacitors have exceptional power density and cyclability. Their energy density can be increased using ionic liquids and electrodes with sub-nanometer pores, but this tends to reduce their power density and compromise the key advantage of supercapacitors. To help address this issue through material optimization, here we unravel the mechanisms of charging sub-nanometer pores with ionic liquids using molecular simulations, navigated by a phenomenological model. We show that charging of ionophilic pores is a diffusive process, often accompanied by overfilling followed by de-filling. In sharp contrast to conventional expectations, charging is fast because ion diffusion during charging can be an order of magnitude faster than in bulk, and charging itself is accelerated by the onset of collective modes. Further acceleration can be achieved using ionophobic pores by eliminating overfilling/de-filling and thus leading to charging behavior qualitatively different from that in conventional, ionophilic pores.

In the recent experiments [Chmiola et al, Science 313, 1760 (2006); Largeot et al, J. Am. Chem. Soc. 130, 2730 (2008)] an anomalous increase of the capacitance with a decrease of the pore size of a carbon-based porous electric double-layer capacitor has been observed. We explain this effect by the image forces which exponentially screen out the electrostatic interactions of ions in the interior of a pore. Packing of ions of the same sign becomes easier and is mainly limited by steric interactions. We call this state `superionic' and suggest a simple model to describe it. The model reveals a possibility of a voltage-induced first-order transition between a cation(anion)-deficient phase and a cation(anion)-rich phase which manifests itself in a jump of capacitance as a function of voltage.

Colloids immersed in a critical or near-critical binary liquid mixture and close to a chemically patterned substrate are subject to normal and lateral critical Casimir forces of dominating strength. For a single colloid we calculate these attractive or repulsive forces and the corresponding critical Casimir potentials within mean-field theory. Within this approach we also discuss the quality of the Derjaguin approximation and apply it to Monte Carlo simulation data available for the system under study. We find that the range of validity of the Derjaguin approximation is rather large and that it fails only for surface structures which are very small compared to the geometric mean of the size of the colloid and its distance from the substrate. For certain chemical structures of the substrate the critical Casimir force acting on the colloid can change sign as a function of the distance between the particle and the substrate; this provides a mechanism for stable levitation at a certain distance which can be strongly tuned by temperature, i.e., with a sensitivity of more than 200nm/K., Comment: 27 pages, 14 figures

Bulk properties of ionic liquid crystals are investigated using density functional theory. The liquid crystal molecules are represented by ellipsoidal particles with charges located in their center or at their tails. Attractive interactions are taken into account in terms of the Gay-Berne pair potential. Rich phase diagrams involving vapor, isotropic and nematic liquid, as well as smectic phases are found. The dependence of the phase behavior on various parameters such as the length of the particles and the location of charges on the particles is studied.

Based on renormalization group concepts and explicit mean field calculations we study the universal contribution to the effective force and torque acting on an ellipsoidal colloidal particle which is dissolved in a critical fluid and is close to a homogeneous planar substrate. At the same closest distance between the substrate and the surface of the particle, the ellipsoidal particle prefers an orientation parallel to the substrate and the magnitude of the fluctuation induced force is larger than if the orientation of the particle is perpendicular to the substrate. The sign of the critical torque acting on the ellipsoidal particle depends on the type of boundary conditions for the order parameter at the particle and substrate surfaces, and on the pivot with respect to which the particle rotates.

We study the normal and lateral effective critical Casimir forces acting on a spherical colloid immersed in a critical binary solvent and close to a chemically structured substrate with alternating adsorption preference. We calculate the universal scaling function for the corresponding potential and compare our results with recent experimental data [Soyka F., Zvyagolskaya O., Hertlein C., Helden L., and Bechinger C., Phys. Rev. Lett., 101, 208301 (2008)]. The experimental potentials are properly captured by our predictions only by accounting for geometrical details of the substrate pattern for which, according to our theory, critical Casimir forces turn out to be a sensitive probe., Comment: 6 pages, 3 figures

We study the phase behavior of a nematic liquid crystal confined between a flat substrate with strong anchoring and a patterned substrate whose structure and local anchoring strength we vary. By first evaluating an effective surface free energy function characterizing the patterned substrate we derive an expression for the effective free energy of the confined nematic liquid crystal. Then we determine phase diagrams involving a homogeneous state in which the nematic director is almost uniform and a hybrid aligned nematic state in which the orientation of the director varies through the cell. Direct minimization of the free energy functional were performed in order to test the predictions of the effective free energy method. We find remarkably good agreement between the phase boundaries calculated from the two approaches. In addition the effective energy method allows one to determine the energy barriers between two states in a bistable nematic device., Comment: 10 pages, 7 figures, submitted

We consider a non-spherical colloidal particle immersed in a fluid close to its critical point. The temperature dependence of the corresponding order parameter profile is calculated explicitly. We perform a systematic expansion of the order parameter profile in powers of the local curvatures of the surface of the colloidal particle. This curvature expansion reduces to the short distance expansion of the order parameter profile in the case that the solvent is at the critical composition., Comment: 9 pages, 7 figures

A nematic liquid crystal in contact with a grating surface possessing an alternating stripe pattern of locally homeotropic and planar anchoring is studied within the Frank--Oseen model. The combination of both chemical and geometrical surface pattern leads to rich phase diagrams, involving a homeotropic, a planar, and a tilted nematic texture. The effect of the groove depth and the anchoring strengths on the location and the order of phase transitions between different nematic textures is studied. A zenithally bistable nematic device is investigated by confining a nematic liquid crystal between the patterned grating surface and a flat substrate with strong homeotropic anchoring., Comment: 7 pages, 7 figures