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We present a method for calculating high-order virial expansions of the isotropic-nematic phase transition which we apply here to hard spheroids. Studying a range of aspect ratios, for both oblate and prolate particles, we obtain equations of state, coexistence densities, and nematic order parameters, using expansions truncated at up to eighth virial level. For particles of large aspect ratios our results show rapid convergence, with truncation at sixth order sufficient to give excellent agreement with simulation data. For more spherical particles the convergence is less rapid, with results for up to eighth-order theory approaching but still not reaching simulation data. Our results indicate that high-order viral expansions are better suited to predicting equations of state than coexistence densities. We also test the validity of using the Onsager trial function to approximate the orientational distribution function, finding only small errors when making this approximation.

The system of hard cut spheres (disk-shaped particles formed by symmetrically truncating the end caps of a sphere) exhibits an intriguing "cubatic" phase with cubic orientational symmetry. However, it is unclear whether this phase is metastable with respect to the columnar phase. We attempt to provide an answer to this question by carrying out free energy calculations by the expanded ensemble Monte Carlo method. We conclude that there may be a very small region of cubatic stability in the vicinity of the isotropic-cubatic phase transition, but that that transition would need to be determined more accurately to obtain a definitive answer. We also comment on the efficacy of the expanded ensemble method for these kinds of calculations.

The phase behavior of a system of hard-cut spheres has been studied using a high-order virial theory and by Monte Carlo simulation. The cut-sphere particles are disks of thickness L formed by symmetrically truncating the end caps of a sphere of diameter D . The virial theory predicts a stable nematic phase for aspect ratio LD=0.1 and a stable cubatic phase for LD=0.15-0.3 . The virial series converges rapidly on the equation of state of the isotropic and nematic phases, while for the cubatic phase the convergence is slower, but still gives good agreement with the simulation at high order. It is found that a high-order expansion (up to B8 ) is required to predict a stable cubatic phase for LD> or =0.15 , indicating the importance of many-body interactions in stabilizing this phase. Previous simulation work on this system has focused on aspect ratios LD=0.1 , 0.2, and 0.3. We expand this to include also LD=0.15 and 0.25, and we introduce a fourth-rank tensor to measure cubatic ordering. We have applied a multiparticle move which dramatically speeds the attainment of equilibrium in the nematic phase and therefore is of great benefit in the study of the isotropic-nematic phase transition. In agreement with the theory, our simulations confirm the stability of the nematic phase for LD=0.1 and the stability of the cubatic phase over the nematic for LD=0.15-0.3 . There is, however, some doubt about the stability of the cubatic phase with respect to the columnar. We have shown that the cubatic phase found on compression at LD=0.1 is definitely metastable, but the results for LD=0.2 were less conclusive.

We study the thermodynamics and the pair structure of hard, infinitely thin, circular platelets in the isotropic phase. Monte Carlo simulation results indicate a rich spatial structure of the spherical expansion components of the direct correlation function, including nonmonotonical variation of some of the components with density. Integral equation theory is shown to reproduce the main features observed in simulations. The hypernetted chain closure, as well as its extended versions that include the bridge function up to second and third order in density, perform better than both the Percus-Yevick closure and Verlet bridge function approximation. Using a recent fundamental measure density functional theory, an analytic expression for the direct correlation function is obtained as the sum of the Mayer bond and a term proportional to the density and the intersection length of two platelets. This is shown to give a reasonable estimate of the structure found in simulations, but to fail to capture the nonmonotonic variation with density. We also carry out a density functional stability analysis of the isotropic phase with respect to nematic ordering and show that the limiting density is consistent with that where the Kerr coefficient vanishes. As a reference system, we compare to simulation results for hard oblate spheroids with small, but nonzero elongations, demonstrating that the case of vanishingly thin platelets is approached smoothly.

The structure of hard rod-disk mixtures is studied using Monte Carlo simulations and integral equation theory, for a range of densities in the isotropic phase. By extension of methods used in single component fluids, the pair correlation functions of the molecules are calculated and comparisons between simulation and integral equation theory, using a number of different closure relations, are made. Comparison is also made for thermodynamic data and phase behavior.

We present the results of Monte Carlo simulations of hard spheroids of revolution of different elongations. Both prolate and oblate shapes are examined. A systematic study of the bridge function b(1,2), and direct comparison with the indirect correlation function gamma(1,2)=h(1,2)-c(1,2) at densities spanning the isotropic fluid range, allow us to evaluate the accuracy of various proposed closure relations for integral equations.

We present methodologies for calculating the direct correlation function c(1,2), the cavity function y(1,2), and the bridge function b(1,2), for molecular liquids, from Monte Carlo simulations. As an example we present results for the isotropic hard spheroid fluid with elongation e = 3. The simulation data are compared with the results from integral equation theory. In particular, we solve the Percus-Yevick and hypernetted chain equations. In addition, we calculate the first two terms in the virial expansion of the bridge function and incorporate this into the closure. At low densities, the bridge functions calculated by theory and from simulation are in good agreement, lending support to the correctness of our numerical procedures. At higher densities, the hypernetted chain results are brought into closer agreement with simulation by incorporating the approximate bridge function, but significant discrepancies remain.