Péter Gurin

Nematic and smectic ordering in a system of two-dimensional hard zigzag particles

The orientational and positional ordering of the two-dimensional system of hard zigzag particles has been investigated by means of Onsager theory. Analytical results are obtained for the transition densities of the isotropic-nematic and the nematic-smectic phase transitions. It is shown that the stability of the nematic and smectic phases is very sensitive to the molecular shape. In the hard needle limit, only the isotropic-nematic phase transition takes place, while increasing the tail length and the bent angle between the central core and the tails destabilizes the nematic phase. On the other hand the stability of the smectic phase is due to the increasing excluded area cost with bent angle and the tail length. The zigzag particles pack in a layered structure such that they are tilted and form semi-ideal gas in the layers to push the high cost excluded area regions into the interstitial regions. The predictions of Onsager theory are in good agreement with MC simulation data.

Spontaneously bended nematic and antiferroelectric smectic structures of banana-shaped hard particles in two dimensions

Spontaneously deformed nematic and antiferroelectric smectic structures have been detected in a two-dimensional system of hard banana-shaped needles by means of Monte Carlo simulation and Onsager theory. The spatially non-uniform and deformed nematic consists of orientationally ordered polar domains, where the nematic director displays mainly bended patterns. The net polarization of the bended nematic is zero. Onsager theory shows that the bent-core structure of the particles favours the bend deformation due to a free energy reducing bend torque, while the splay deformation results in a free energy cost. With increasing pressure the polar nematic domains becomes thinner and transforms into linear arrays with alternating polarity (antiferroelectric smectic phase). The theoretical results are in good agreement with the simulations.

Pair correlation functions of two- and three-dimensional hard-core fluids confined into narrow pores: exact results from transfer-matrix method.

The effect of confinement is studied on the local structure of two- and three-dimensional hard-core fluids. The hard disks are confined between two parallel lines, while the hard spheres are in a cylindrical hard pore. In both cases only nearest neighbour interactions are allowed between the particles. The vertical and longitudinal pair correlation functions are determined by means of the exact transfer-matrix method. The vertical pair correlation function indicates that the wall induced packing constraint gives rise to a zigzag (up-down sequence) shaped close packing structure in both two- and three-dimensional systems. The longitudinal pair correlation function shows that both systems transform continuously from a one-dimensional gas-like behaviour to a zigzag solid-like structure with increasing density.

Structural properties of hard disks in a narrow tube

Positional ordering of a two-dimensional fluid of hard disks is examined in tubes so narrow that only nearest neighbor interactions take place. Using the exact transfer-matrix method the transverse and longitudinal pressure components and the correlation function are determined numerically. Fluid–solid phase transition does not occur even in the widest tube, where the method just loses its exactness, but the appearance of a dramatic change in the equation of state and the longitudinal correlation function shows that the system undergoes a structural change from a fluid to a solid-like order. The pressure components show that the collisions are dominantly longitudinal at low densities, while they are transverse in the vicinity of the close packing density. The transverse correlation function shows that the size of solid-like domains grows exponentially with increasing pressure and the correlation length diverges at close packing. It is possible to find an analytically solvable model by expanding the contact distance up to first order. The approximate model, which corresponds to a system of hard parallel rhombuses, behaves very similarly to the system of hard disks.

Phase behaviour and correlations of parallel hard squares: from highly confined to bulk systems

We study a fluid of two-dimensional parallel hard squares in bulk and under confinement in channels, with the aim of evaluating the performance of fundamental-measure theory (FMT). To this purpose, we first analyse the phase behaviour of the bulk system using FMT and Percus-Yevick (PY) theory, and compare the results with molecular dynamics and Monte Carlo simulations. In a second step, we study the confined system and check the results against those obtained from the transfer matrix method and from our own Monte Carlo simulations. Squares are confined to channels with parallel walls at angles of 0° or 45° relative to the diagonals of the parallel hard squares, respectively, which allows for an assessment of the effect of the external-potential symmetry on the fluid structural properties. In general FMT overestimates bulk correlations, predicting the existence of a columnar phase (absent in simulations) prior to crystallization. The equation of state predicted by FMT compares well with simulations, although the PY approach with the virial route is better in some range of packing fractions. The FMT is highly accurate for the structure and correlations of the confined fluid due to the dimensional crossover property fulfilled by the theory. Both density profiles and equations of state of the confined system are accurately predicted by the theory. The highly non-uniform pair correlations inside the channel are also very well described by FMT.

Beyond the single-file fluid limit using transfer matrix method: Exact results for confined parallel hard squares

We extend the transfer matrix method of one-dimensional hard core fluids placed between confining walls for that case where the particles can pass each other and at most two layers can form. We derive an eigenvalue equation for a quasi-one-dimensional system of hard squares confined between two parallel walls, where the pore width is between σ and 3σ (σ is the side length of the square). The exact equation of state and the nearest neighbor distribution functions show three different structures: a fluid phase with one layer, a fluid phase with two layers, and a solid-like structure where the fluid layers are strongly correlated. The structural transition between differently ordered fluids develops continuously with increasing density, i.e., no thermodynamic phase transition occurs. The high density structure of the system consists of clusters with two layers which are broken with particles staying in the middle of the pore.

Towards understanding the ordering behavior of hard needles: Analytical solutions in one dimension

We re-examine the ordering behavior of a one-dimensional fluid of freely rotating hard needles, where the centers of mass of the particles are restricted to a line. Analytical equations are obtained for the equation of state, order parameter, and orientational correlation functions using the transfer-matrix method if some simplifying assumptions are applied for either the orientational freedom or the contact distance between two needles. The two-state Zwanzig model accounts for the orientational ordering, but it produces unphysical pressure at high densities and there is no orientational correlation. The four-state Zwanzig model gives reasonable results for orientational correlation function, but the pressure is still poorly represented at high densities. In the continuum limit, apart from the orientational correlation length it is managed to reproduce all relevant bulk properties of the hard needles using an approximate formula for the contact distance. The results show that the orientational correlation length diverges at zero and infinite pressures. The high-density behavior of the fluid of needles is not resolved.

Critical behavior of hard squares in strong confinement

We examine the phase behavior of a quasi-one-dimensional system of hard squares with side-length σ, where the particles are confined between two parallel walls and only nearest-neighbor interactions occur. As in our previous work [Gurin, Varga, and Odriozola, Phys. Rev. E 94, 050603 (2016)]2470-004510.1103/PhysRevE.94.050603, the transfer operator method is used, but here we impose a restricted orientation and position approximation to yield an analytic description of the physical properties. This allows us to study the parallel fluid-like to zigzag solid-like structural transition, where the compressibility and heat capacity peaks sharpen and get higher as H→H_{c}=2sqrt[2]-1≈1.8284 and p→p_{c}=∞. Here H is the width of the channel measured in σ units and p is the pressure. We have found that this structural change becomes critical at the (p_{c},H_{c}) point. The obtained critical exponents belong to the universality class of the one-dimensional Ising model. We believe this behavior holds for the unrestricted orientational and positional case.

Ordering of hard rectangles in strong confinement

Using transfer operator and fundamental measure theories, we examine the structural and thermodynamic properties of hard rectangles confined between two parallel hard walls. The side lengths of the rectangle (L and D, L>D) and the pore width (H) are chosen such that a maximum of two layers is allowed to form when the long sides of the rectangles are parallel to the wall, while only one layer is possible in case the rectangles are perpendicular to the wall. We observe three different structures: (i) at low density, the rectangles align mainly parallel to the wall, (ii) at intermediate or high density, two fluid layers form in which the rectangles are parallel to the wall, and (iii) a dense single fluid layer with rectangles aligned mainly perpendicular to the wall. The transition between these structures is smooth without any non-analytic behaviour in the thermodynamic quantities; however, the fraction of particles perpendicular (or parallel) to the wall can exhibit a relatively sudden change if L is close to H. In this case, interestingly, even three different structures can be observed with increasing density.

Ordering transitions of weakly anisotropic hard rods in narrow slitlike pores

The effect of strong confinement on the positional and orientational ordering is examined in a system of hard rectangular rods with length L and diameter D (L>D) using the Parsons-Lee modification of the second virial density-functional theory. The rods are nonmesogenic (L/D<3) and confined between two parallel hard walls, where the width of the pore (H) is chosen in such a way that both planar (particles long axis parallel to the walls) and homeotropic (particles long axis perpendicular to the walls) orderings are possible and a maximum of two layers is allowed to form in the pore. In the extreme confinement limit of H≤2D, where only one-layer structures appear, we observe a structural transition from a planar to a homeotropic fluid layer with increasing density, which becomes sharper as L→H. In wider pores (2D<H<3D) planar order with two layers, homeotropic order, and even combined bilayer structures (one layer is homeotropic, while the other is planar) can be stabilized at high densities. Moreover, first-order phase transitions can be seen between different structures. One of them emerges between a monolayer and a bilayer with planar orders at relatively low packing fractions.