Hard Ellipsoids Research Articles

A critical examination of the decoupling approximation for small-angle scattering from hard ellipsoids of revolution

The decoupling approximation, proposed by Kotlarchyk & Chen [J. Chem. Phys. (1983), 79, 2461–2469], is a first-order correction to the experimentally determined apparent structure factor that is necessary because of concentration effects in polydisperse and/or nonspherical systems. While the approximation is considered accurate for spheres with low polydispersity (<10%), the corresponding limitations for nonspherical particles are unknown. The validity of this approximation is studied for monodisperse dispersions of hard ellipsoids of revolution with aspect ratios ranging from 0.333 to 3 and a guide for its accuracy is provided.

Shear-rate-dependent viscosities of nematic and disc-like particles perfectly aligned in arbitrary relative directions to the shear layer

The shear-rate-dependent viscosity coefficients of hard ellipsoids are derived for arbitrary relative orientations to the shear flow geometry. Each of the nine components of the coefficients scaled by the Newtonian shear viscosity agrees with the previous result for the viscosity in the zero-shear-rate limit. Among the components, the shear viscosity is graphically displayed for nematic ellipsoids with an axis ratio greater than 1 and for disc-like ellipsoids with an axis ratio less than 1 over the whole range of relative orientations of the axis of ellipsoid to the plane shear layer. As the primary axis of the ellipsoid rotates from the x-axis to the y-axis in the x-y plane, the shear viscosity increases or decreases for nematic or disc-like ellipsolids, respectively.

Confinement Induced Ordering in Fluid of Hard Ellipsoids

The ordering configurations of a fluid of anisotropic ellipsoids under the confinement of two apposing impenetrable walls are studied by Monte Carlo simulations. The excess adsorption of the fluid on the walls with respect to the aspect ratio has a maximum at the critical aspect ratio of 2.9 in high-density ellipsoid fluids, indicating an orientational ordering in the adjacent region of the walls, which is confirmed by probing into the density configurations and the orientational order parameter in the adjacent region of the walls for varying aspect ratios. In addition, the orientational order parameter in the bulk fluid at the same density is calculated, and it indicates an isotropic state as the bulk density is still below the bulk isotropic-to-nematic transition. Therefore, it can be concluded that the anisotropic ordering near the walls in the ellipsoid fluid that exhibits isotropic in the bulk is induced by the confinement effect of the walls.

Effect of orientational restriction on monolayers of hard ellipsoids.

The effect of out-of-plane orientational freedom on the orientational ordering properties of a monolayer of hard ellipsoids is studied using the Parsons-Lee scaling approach and replica exchange Monte Carlo computer simulation. Prolate and oblate ellipsoids exhibit very different ordering properties, namely, the axes of revolution of prolate particles tend to lean out, while those of oblate ones prefer to lean into the confining plane. The driving mechanism of this is that the particles try to maximize the available free area on the confining surface, which can be achieved by minimizing the cross section areas of the particles with the plane. In the lack of out-of-plane orientational freedom the monolayer of prolate particles is identical to a two-dimensional hard ellipse system, which undergoes an isotropic-nematic ordering transition with increasing density. With gradually switching on the out-of-plane orientational freedom the prolate particles lean out from the confining plane and destabilisation of the in-plane isotropic-nematic phase transition is observed. The system of oblate particles behaves oppositely to that of prolates. It corresponds to a two-dimensional system of hard disks in the lack of out-of-plane freedom, while it behaves similar to that of hard ellipses in the freely rotating case. Solid phases can be realised by lower surface coverage due to the out-of-plane orientation freedom for both oblate and prolate shapes.

Hard convex lens-shaped particles: Densest-known packings and phase behavior.

By using theoretical methods and Monte Carlo simulations, this work investigates dense ordered packings and equilibrium phase behavior (from the low-density isotropic fluid regime to the high-density crystalline solid regime) of monodisperse systems of hard convex lens-shaped particles as defined by the volume common to two intersecting congruent spheres. We show that, while the overall similarity of their shape to that of hard oblate ellipsoids is reflected in a qualitatively similar phase diagram, differences are more pronounced in the high-density crystal phase up to the densest-known packings determined here. In contrast to those non-(Bravais)-lattice two-particle basis crystals that are the densest-known packings of hard (oblate) ellipsoids, hard convex lens-shaped particles pack more densely in two types of degenerate crystalline structures: (i) non-(Bravais)-lattice two-particle basis body-centered-orthorhombic-like crystals and (ii) (Bravais) lattice monoclinic crystals. By stacking at will, regularly or irregularly, laminae of these two crystals, infinitely degenerate, generally non-periodic in the stacking direction, dense packings can be constructed that are consistent with recent organizing principles. While deferring the assessment of which of these dense ordered structures is thermodynamically stable in the high-density crystalline solid regime, the degeneracy of their densest-known packings strongly suggests that colloidal convex lens-shaped particles could be better glass formers than colloidal spheres because of the additional rotational degrees of freedom.

Granular gas of ellipsoids: analytical collision detection implemented on GPUs

We present a hybrid GPU-CPU implementa- tion of an accurate discrete element model for a system of ellipsoids. The ellipsoids have three translational degrees of freedom, their rotational motion being described through quaternions and the contact interaction between two ellip- soids is described by a force which accounts for the elastic and dissipative interactions. Further we combine the exact derivation of contact points between ellipsoids (Wang et al. in Computing 72(1-2):235-246, 2004) with the advantages oftheGPU-NVIDIAparallelizationstrategy(Owensetal.in ComputGraphForum26:80-113,2007).Thisnoveltymakes theanalyticalalgorithmcomputationally feasiblewhendeal- ing with several thousands of particles. As a benchmark, we simulate a granular gas of frictionless ellipsoids identifying a classical homogeneous cooling state for ellipsoids. For low dissipative systems, the behavior of the granular temperature indicates that the cooling dynamics is governed by the elon- gation of the ellipsoids and the restitution coefficient. Our outcomes comply with the statistical mechanical laws and the results are in agreement with previous findings for hard ellipsoids (Bereolos et al. in J Chem Phys 99:6087, 1993; VillemotandTalbotinGranulMatter14:91-97,2012).Addi- tionally, new insight is provided namely suggesting that the mean field description of the cooling dynamics of elongated particles is conditioned by the particle shape and the degree of energy equipartition.

Strong effect of weak charging in suspensions of anisotropic colloids.

Suspensions of hard colloidal particles frequently serve as model systems in studies on fundamental aspects of phase transitions. But often colloidal particles that are considered as "hard" are in fact weakly charged. If the colloids are spherical, weak charging has only a weak effect on the structural properties of the suspension, which can be easily corrected for. However, this does not hold for anisotropic particles. We introduce a model for the interaction potential between charged ellipsoids of revolution (spheroids) based on the Derjaguin approximation of Debye-Hückel theory and present a computer simulation study on aspects of the system's structural properties and phase behaviour. In line with previous experimental observations, we find that even a weak surface charge has a strong impact on the correlation functions. A likewise strong impact is seen on the phase behaviour, in particular, we find stable cubatic order in suspensions of oblate ellipsoids.

Crystallization in glassy suspensions of hard ellipsoids

We have carried out computer simulations of overcompressed suspensions of hard monodisperse ellipsoids and observed their crystallization dynamics. The system was compressed very rapidly in order to reach the regime of slow, glass-like dynamics. We find that, although particle dynamics become sub-diffusive and the intermediate scattering function clearly develops a shoulder, crystallization proceeds via the usual scenario: nucleation and growth for small supersaturations, spinodal decomposition for large supersaturations. In particular, we compared the mobility of the particles in the regions where crystallization set in with the mobility in the rest of the system. We did not find any signature in the dynamics of the melt that pointed towards the imminent crystallization events.

Random generation of periodic hard ellipsoids based on molecular dynamics: A computationally-efficient algorithm

This paper presents a computationally-efficient algorithm for generating random periodic packings of hard ellipsoids. The algorithm is based on molecular dynamics where the ellipsoids are set in translational and rotational motion and their volumes gradually increase. Binary collision times are computed by simply finding the roots of a non-linear function. In addition, an original and efficient method to compute the collision time between an ellipsoid and a cube face is proposed. The algorithm can generate all types of ellipsoids (prolate, oblate and scalene) with very high aspect ratios (i.e., >10). It is the first time that such packings are reported in the literature. Orientations tensors were computed for the generated packings and it has been shown that ellipsoids had a uniform distribution of orientations. Moreover, it seems that for low aspect ratios (i.e., ⩽10), the volume fraction is the most influential parameter on the algorithm CPU time. For higher aspect ratios, the influence of the latter becomes as important as the volume fraction. All necessary pseudo-codes are given so that the reader can easily implement the algorithm.

“Ideal glassformers” vs “ideal glasses”: Studies of crystal-free routes to the glassy state by “potential tuning” molecular dynamics, and laboratory calorimetry

The ability of some liquids to vitrify during supercooling is usually seen as a consequence of the rates of crystal nucleation (and∕or crystal growth) becoming small [D. R. Uhlmann, J. Non-Cryst. Solids 7, 337 (1972)]--and thus a matter of kinetics. However, there is evidence dating back to the empirics of coal briquetting for maximum trucking efficiency [D. Frenkel, Physics 3, 37 (2010)] that some object shapes find little advantage in self-assembly to ordered structures--meaning random packings prevail. Noting that key studies of non-spherical object packing have never been followed from hard ellipsoids [A. Donev, F. H. Stillinger, P. M. Chaikin, and S. Torquato, Phys. Rev. Lett. 92, 255506 (2004); A. Donev, I. Cisse, D. Sachs, E. A. Variano, F. H. Stillinger, R. Connelly, S. Torquato, and P. M. Chaikin, Science 303, 990 (2004)] or spherocylinders [S. R. Williams and A. P. Philipse, Phys. Rev. E 67, 051301 (2003)] (diatomics excepted [S.-H. Chong, A. J. Moreno, F. Sciortino, and W. Kob, Phys. Rev. Lett. 94, 215701 (2005)] into the world of molecules with attractive forces, we have made a molecular dynamics study of crystal melting and glass formation on the Gay-Berne (G-B) model of ellipsoidal objects [J. G. Gay and B. J. Berne, J. Chem. Phys. 74, 3316 (1981)] across the aspect ratio range of the hard ellipsoid studies. Here, we report that in the aspect ratio range of maximum ellipsoid packing efficiency, various G-B crystalline states that cannot be obtained directly from the liquid, disorder spontaneously near 0 K and transform to liquids without any detectable enthalpy of fusion. Without claiming to have proved the existence of single component examples, we use the present observations, together with our knowledge of non-ideal mixing effects, to discuss the probable existence of "ideal glassformers"--single or multicomponent liquids that vitrify before ever becoming metastable with respect to crystals. We find evidence that "ideal glassformer" systems might also be highly fragile systems, approaching the "ideal glass" condition. We link this to the high "volume fragility" behavior observed in recent hard dumbbell studies at similar length∕diameter ratios [R. Zhang and K. S. Schweitzer, J. Chem. Phys. 133, 104902 (2010)]. The discussion suggests some unusual systems for laboratory study. Using differential scanning calorimetry detection of fusion points T(m), liquidus temperatures T(l), and glass transition temperatures T(g), we describe a system that would seem incapable of crystallizing before glass transition, i.e., an "ideal glassformer." The existence of crystal-free routes to the glassy state will eliminate precrystalline fluctuations as a source of the dynamic heterogeneities that are generally considered important in the discussion of the "glassy state problem [P. W. Anderson, Science 267, 1615 (1995)]."

Further details on the phase diagram of hard ellipsoids of revolution

In recent work we revisited the phase diagram of hard ellipsoids of revolution (spheroids) by means of replica exchange Monte Carlo simulations. This was done by setting random initial configurations, and allows to confirm the formation of sm2 crystal structures at high densities [P. Pfleiderer and T. Schilling, Phys. Rev. E 75, 020402 (2007)] for large anisotropies and stretched-fcc for small anisotropies. In this work we employed the same technique but setting the starting cells as sm2 crystal structures having the maximum known packing density [A. Donev, F. H. Stillinger, P. M. Chaikin, and S. Torquato, Phys. Rev. Lett. 92, 255506 (2004)]. This procedure yields a very rich behavior for quasi-spherical oblates and prolates. These systems, from low to high pressures, show the following phases: isotropic fluid, plastic solid, stretched-fcc solid, and sm2 solid. The first three transitions are first order, whereas the last one is a subtle, probably high order transition. This picture is consistent with the fact of having the sm2 structure capable of producing the maximally achievable density.

Towards understanding the empty liquid of colloidal platelets: vapour–liquid phase coexistence of square-well oblate ellipsoids

We study the phase behaviour of hard oblate ellipsoids with superimposed short-ranged oblate-shaped square-well attractions using the replica exchange Monte Carlo method and a simple van der Waals type perturbation theory. By fixing the square-well range (λ = 0.25σ‖), we examine the effect of varying the oblates aspect ratio, k = σ⊥/σ‖, on the density profiles, vapour–liquid and isotropic–nematic phase transitions. We observe that the formation of a liquid phase with vanishing density, an empty liquid, is possible with increasing aspect ratio. Surprisingly, the increasing shape anisotropy does not shift the stability region of the nematic phase to low densities, while the oblate-shaped square-well attraction favours disordered states. For k > 1.5, the critical temperature and packing fraction monotonically decrease with k, while the isotropic–nematic phase boundary moves towards higher packing fractions with decreasing temperature for all k. Simulations show that oblates preferably orientate their faces parallel to the vapour–liquid interface when located at the liquid side of the interface region and perpendicular when located at the vapour side.

Empty liquid state and self-assembly of high valence non-spherical colloidal systems

A vapour–liquid phase coexistence with vanishing critical volume fraction (empty liquid) is predicted in some model systems of attractive hard ellipsoids. The trends in critical density and temperature do not depend on the ellipsoid shape and the range of the square-well attraction. Our theoretical and simulation studies show transparently that the empty liquid limit is due to the competition between the anisotropic attractive and repulsive interactions. Additionally, the nematic phase is destabilized by the square-well attraction for both prolate and oblate shapes. The demand to maximize the number of bonds while keeping a relatively low excluded volume leads to special structures such as the cubatic and star-shaped cluster phases at low temperatures. The liquid branch of the vapour–liquid binodal is always isotropic for oblates, while it can be isotropic or cluster-like for prolates. Our results predict the occurrence of an empty liquid state in high valence anisotropic colloidal systems.

Revisiting the phase diagram of hard ellipsoids

In this work, the well-known Frenkel-Mulder phase diagram of hard ellipsoids of revolution [D. Frenkel and B. M. Mulder, Mol. Phys. 55, 1171 (1985)] is revisited by means of replica exchange Monte Carlo simulations. The method provides good sampling of dense systems and so, solid phases can be accessed without the need of imposing a given structure. At high densities, we found plastic solids and fcc-like crystals for semi-spherical ellipsoids (prolates and oblates), and SM2 structures [P. Pfleiderer and T. Schilling, Phys. Rev. E 75, 020402 (2007)] for x : 1-prolates and 1 : x-oblates with x ≥ 3. The revised fluid-crystal and isotropic-nematic transitions reasonably agree with those presented in the Frenkel-Mulder diagram. An interesting result is that, for small system sizes (100 particles), we obtained 2:1- and 1.5:1-prolate equations of state without transitions, while some order is developed at large densities. Furthermore, the symmetric oblate cases are also reluctant to form ordered phases.

Homogeneous cooling of hard ellipsoids

We study the homogeneous cooling of hard, smooth ellipsoids in three dimensions using event driven numerical simulation. The elongation of the particle has a strong effect on the cooling behavior. Weakly elongated ellipsoids display two distinct cooling regimes. For small times, the translational and rotational energy decay at a different rates. Once their ratio reaches a time-independent value (different from equipartition), the overall temperature of the system decays like t−2, as predicted by Haff’s law. For more elongated ellipsoids the translational and rotational temperatures rapidly reach a constant ratio near unity. The cooling behavior in the homogeneous state can be predicted from Haff’s law and the equilibrium collision rate.

Перколяция вытянутых эллипсоидов вращения в континууме

Continuum percolation of the hard prolate ellipsoids of rotation with permeable shell has been investigated. It is the model of phase transition sol–gel. Ellipsoids are located in the cube randomly. For each set of parameters 100 tests are spent. For each test the finding of the percolation cluster is the main task. The fraction of the packing for which the probability of the percolation cluster appearance is equal 0.5, is called a percolation threshold. Value of the percolation threshold corresponds to the gel point. Dependence of value of the percolation threshold on thickness of permeable shell and aspect ratio has been obtained. In addition to the percolation threshold the other characteristics of the model have been obtained, such as: the size distribution of clusters, the average cluster size, the strength and the fractal dimension of the percolation cluster, the average value and the distribution of neighbors of an element, the critical exponents.

Hard ellipsoids: Analytically approaching the exact overlap distance

Following previous work [G. Odriozola and F. de J. Guevara-Rodríguez, J. Chem. Phys. 134, 201103 (2011)], the replica exchange Monte Carlo technique is used to produce the equation of state of hard 1:5 aspect-ratio oblate ellipsoids for a wide density range. Here, in addition to the analytical approximation of the overlap distance given by Berne and Pechukas (BP) and the exact numerical solution of Perram and Wertheim, we tested a simple modification of the original BP approximation (MBP) which corrects the known T-shape mismatch of BP for all aspect ratios. We found that the MBP equation of state shows a very good quantitative agreement with the exact solution. The MBP analytical expression allowed us to study size effects on the previously reported results. For the thermodynamic limit, we estimated the exact 1:5 hard ellipsoid isotropic-nematic transition at the volume fraction 0.343 ± 0.003, and the nematic-solid transition in the volume fraction interval (0.592 ± 0.006)-(0.634 ± 0.008).

Communication: Equation of state of hard oblate ellipsoids by replica exchange Monte Carlo

We implemented the replica exchange Monte Carlo technique to produce the equation of state of hard 1:5 aspect-ratio oblate ellipsoids for a wide density range. For this purpose, we considered the analytical approximation of the overlap distance given by Bern and Pechukas and the exact numerical solution given by Perram and Wertheim. For both cases we capture the expected isotropic-nematic transition at low densities and a nematic-crystal transition at larger densities. For the exact case, these transitions occur at the volume fraction 0.341, and in the interval 0.584-0.605, respectively.

A TWO-COMPONENT FLUID MIXTURE OF THE HARD SPHEROCYLINDERS

We study a classical fluid mixture of nonspherical molecules. The components of the mixture are two kinds of the hard spherocylinders with different shape anisotropies L/D. Two different approaches are used to calculate the direct correlation functions (DCF) of this kind of fluids. First, we use a formalism based on the weighted density functional theory (WDFT), introduced by Chamoux and Perera [ J. Chem. Phys.104, 1493 (1996)]. Second, we describe a general approach solving the Percus–Yevick (PY) and the hypernetted chain integral equation numerically for the fluid mixtures of hard nonspherical particles. In the second approach, the pair, total, and DCF of binary molecular fluid mixtures can be calculated simultaneously whereas in the WDFT, the pair and the total correlation functions are calculated indirectly. The obtained correlation functions are compared using these two methods. The pressure of the fluid mixture is also calculated using the Fourier zero components of the DCFs and compared with the Monte Carlo simulation. Finally, the large and small shape anisotropy, are considered and the results are compared with the binary fluid mixture of hard ellipsoids and hard spheres. The results are fairly in agreement.

Density functional theory of liquid crystals and surface anchoring: Hard Gaussian overlap-sphere and hard Gaussian overlap-surface potentials

This article applies the density functional theory to confined liquid crystals, comprised of ellipsoidal shaped particles interacting through the hard Gaussian overlap (HGO) potential. The extended restricted orientation model proposed by Moradi and co-workers [J. Phys.: Condens. Matter 17, 5625 (2005)] is used to study the surface anchoring. The excess free energy is calculated as a functional expansion of density around a reference homogeneous fluid. The pair direct correlation function (DCF) of a homogeneous HGO fluid is approximated, based on the optimized sum of Percus-Yevick and Roth DCF for hard spheres; the anisotropy introduced by means of the closest approach parameter, the expression proposed by Marko [Physica B 392, 242 (2007)] for DCF of HGO, and hard ellipsoids were used. In this study we extend an our previous work [Phys. Rev. E 72, 061706 (2005)] on the anchoring behavior of hard particle liquid crystal model, by studying the effect of changing the particle-substrate contact function instead of hard needle-wall potentials. We use the two particle-surface potentials: the HGO-sphere and the HGO-surface potentials. The average number density and order parameter profiles of a confined HGO fluid are obtained using the two particle-wall potentials. For bulk isotropic liquid, the results are in agreement with the Monte Carlo simulation of Barmes and Cleaver [Phys. Rev. E 71, 021705 (2005)]. Also, for the bulk nematic phase, the theory gives the correct density profile and order parameter between the walls.