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This paper explores how competing interactions in the intermolecular potential of fluids affect their structural transitions. The study employs a versatile potential model with a hard core followed by two constant steps, representing wells or shoulders, analyzed in both one-dimensional (1D) and three-dimensional (3D) systems. Comparing these dimensionalities highlights the effect of confinement on structural transitions. Exact results are derived for 1D systems, while the Rational-Function Approximation is used for unconfined 3D fluids. Both scenarios confirm that when the steps are repulsive, the wavelength of the oscillatory decay of the total correlation function evolves with temperature either continuously or discontinuously. In the latter case, a discontinuous oscillation crossover line emerges in the temperature--density plane. For an attractive first step and a repulsive second step, a Fisher--Widom line appears. Although the 1D and 3D results share common features, dimensionality introduces differences: these behaviors occur in distinct temperature ranges, require deeper wells, or become attenuated in 3D. Certain features observed in 1D may vanish in 3D. We conclude that fluids with competing interactions exhibit a rich and intricate pattern of structural transitions, demonstrating the significant influence of dimensionality and interaction features., Comment: 18 pages, 8 figures

In the statistical mechanics approach to liquid-state theory, understanding the role of the intermolecular potential in determining thermodynamic and structural properties is crucial. The Fisher--Widom (FW) line, which separates regions in the temperature vs density plane where the decay of the total correlation function is monotonic or oscillatory, provides insights into the dominance of the attractive or repulsive part of the interactions. Stopper et al. have recently conjectured [J. Chem. Phys. \textbf{151}, 014501 (2019)] that the line of vanishing excess isothermal compressibility approximates the FW line in simple fluids. Here, we investigate this conjecture using the Jagla potential and also explore the line of vanishing excess pressure. We employ theoretical approximations and Monte Carlo simulations to study one-dimensional and three-dimensional systems. While exact results for the one-dimensional case do not support the conjecture, our Monte Carlo simulations for the three-dimensional fluid validate it. Our findings not only contribute to the understanding of the relationship between the three transition lines but also provide valuable insights into the thermodynamic and structural behaviour of simple fluids., Comment: 17 pages, 5 figures; v2: addition of the Widom line plus other minor changes. Rull-Abascal Special Issue for Statistical Physics in Spain

In a previous work, a simple approach to derive the jamming packing fraction of a hard-sphere mixture from the knowledge of the random close-packing fraction of the monocomponent system was proposed. Now, an extension of that approach is applied to provide an approximate formula for the densest packing fraction of a given hard-sphere mixture in terms of the fcc close-packing fraction of a monocomponent hard-sphere system and of a single parameter encapsulating the dependence on the size ratios and the number of spheres in the unit cell. Comparison with recent results for such densest packing fraction of binary and ternary systems is performed and reasonable agreement is obtained., Comment: 6 pages, 1 figure; v2: a few references added

For molecular dynamics simulations of hard particles, we define dynamic neighbors as the distinct particles that collide with a given reference one during a specific time interval. This definition allows us to determine the distribution of the number of dynamic neighbors, its average, and its standard deviation. We will show that regardless of the time window used to identify dynamic neighbors, their distribution is correlated with diffusion coefficients, structure, and configurational entropy. Thus, it is likely that the distribution of the number of dynamic neighbors may be employed as another tool to gain insights into the dynamic behavior of hard systems. We tested this approach on 2D and 3D systems consisting of monodisperse and binary mixtures of hard disks and spheres. Results show that implementing dynamic neighbors to define order parameters can sharpen the signals where transitions take place., Comment: 11 pages, 9 figures

The structural and thermodynamic properties of fluids whose molecules interact via potentials with a hard-core plus a square well, a square shoulder, and a second square well, are considered. Those properties are derived by using a (semi-analytical) rational-function approximation method as a particular case of the more general formulation provided earlier involving potentials with a hard-core plus $n$ piecewise constant sections. Comparison of the results with recent simulation data confirms the usefulness of the approach., Comment: 13 pages, 6 figures. Special Issue: "On the progress of understanding liquids, solutions and interfaces - In Memory of Douglas Henderson." Published version freely accesible until Septembre 25, 2022 from https://authors.elsevier.com/a/1fXa1c8qpWhDB

An analysis of the direct correlation functions $c_{ij} (r)$ of binary additive hard-sphere mixtures of diameters $\sigma_s$ and $\sigma_b$ (where the subscripts $s$ and $b$ refer to the "small" and "big" spheres, respectively), as obtained with the rational-function approximation method and the WM scheme introduced in previous work [S.\ Pieprzyk \emph{et al.}, Phys.\ Rev.\ E {\bf 101}, 012117 (2020)], is performed. The results indicate that the functions $c_{ss}(r<\sigma_s)$ and $c_{bb}(r<\sigma_b)$ in both approaches are monotonic and can be well represented by a low-order polynomial, while the function $c_{sb}(r<\frac{1}{2}(\sigma_b+\sigma_s))$ is not monotonic and exhibits a well defined minimum near $r=\frac{1}{2}(\sigma_b-\sigma_s)$, whose properties are studied in detail. Additionally, we show that the second derivative $c_{sb}''(r)$ presents a jump discontinuity at $r=\frac{1}{2}(\sigma_b-\sigma_s)$ whose magnitude satisfies the same relationship with the contact values of the radial distribution function as in the Percus-Yevick theory., Comment: 11 pages, 8 figures

The structural properties of additive binary hard-sphere mixtures are addressed as a follow-up of a previous paper [S. Pieprzyk et al., Phys. Rev. E 101, 012117 (2020)]. The so-called rational-function approximation method and an approach combining accurate molecular dynamics simulation data, the pole structure representation of the total correlation functions, and the Ornstein-Zernike equation are considered. The density, composition, and size-ratio dependencies of the leading poles of the Fourier transforms of the total correlation functions $h_{ij} (r)$ of such mixtures are presented, those poles accounting for the asymptotic decay of $h_{ij} (r)$ for large $r$. Structural crossovers, in which the asymptotic wavelength of the oscillations of the total correlation functions changes discontinuously, are investigated. The behavior of the structural crossover lines as the size ratio and densities of the two species are changed is also discussed., Comment: 15 pages, 12 figures

This Perspective article provides an overview of some of our analytical approaches to the computation of the structural and thermodynamic properties of single-component and multicomponent hard-sphere fluids. For the structural properties, they yield a thermodynamically consistent formulation, thus improving and extending the known analytical results of the Percus--Yevick theory. Approximate expressions linking the equation of state of the single-component fluid to the one of the multicomponent mixture are also discussed., Comment: 34 pages, 10 figures; v2: Minor changes. Featured in https://aip.scitation.org/action/doSearch? SeriesKey=jcp&AllField=10.1063%2F5.0023903&ConceptID=19590&quickLinkYear=&quickLinkVolume=. arXiv admin note: text overlap with arXiv:0704.0157

New proposals for the equation of state of four- and five-dimensional hard-hypersphere mixtures in terms of the equation of state of the corresponding monocomponent hard-hypersphere fluid are introduced. Such proposals (which are constructed in such a way so as to yield the exact third virial coefficient) extend, on the one hand, recent similar formulations for hard-disk and (three-dimensional) hard-sphere mixtures and, on the other hand, two of our previous proposals also linking the mixture equation of state and the one of the monocomponent fluid but unable to reproduce the exact third virial coefficient. The old and new proposals are tested by comparison with published molecular dynamics and Monte Carlo simulation results and their relative merit is evaluated, Comment: 18 pages, 8 figures; this article belongs to the Special Issue Statistical Mechanics and Thermodynamics of Liquids and Crystals

A system of smooth "frozen" Janus-type disks is studied. Such disks cannot rotate and are divided by their diameter into two sides of different inelasticities. Taking as a reference a system of colored elastic disks, we find differences in the behavior of the collisions once the anisotropy is included. A homogeneous state, akin to the homogeneous cooling state of granular gases, is seen to arise and the singular behavior of both the collisions and the precollisional correlations are highlighted.

The structural properties of the Jagla fluid are studied by Monte Carlo (MC) simulations, numerical solutions of integral equation theories, and the (semi-analytical) rational-function approximation (RFA) method. In the latter case, the results are obtained from the assumption (supported by our MC simulations) that the Jagla potential and a potential with a hard core plus an appropriate piecewise constant function lead to practically the same cavity function. The predictions obtained for the radial distribution function, $g(r)$, from this approach are compared against MC simulations and integral equations for the Jagla model, and also for the limiting cases of the triangle-well potential and the ramp potential, with a general good agreement. The analytical form of the RFA in Laplace space allows us to describe the asymptotic behavior of $g(r)$ in a clean way and compare it with MC simulations for representative states with oscillatory or monotonic decay. The RFA predictions for the Fisher--Widom and Widom lines of the Jagla fluid are obtained., Comment: 12 pages, 10 figures; v2: structure factor included

Values of the fifth virial coefficient, compressibility factors, and fluid-fluid coexistence curves of binary asymmetric nonadditive mixtures of hard disks are reported. The former correspond to a wide range of size ratios and positive nonadditivities and have been obtained through a standard Monte Carlo method for the computation of the corresponding cluster integrals. The compressibility factors as functions of density, derived from canonical Monte Carlo simulations, have been obtained for two values of the size ratio ($q=0.4$ and $q=0.5$), a value of the nonadditivity parameter $\Delta=0.3$), and five values of the mole fraction of the species with the biggest diameter ($x_1=0.1$, $0.3$, $0.5$, $0.7$, and $0.9$). Some points of the coexistence line relative to the fluid-fluid phase transition for the same values of the size ratios and nonadditivity parameter have been obtained from Gibbs Ensemble Monte Carlo simulations. A comparison is made between the numerical results and those that follow from some theoretical equations of state., Comment: 11(+4) pages, 11 figures; Supplemental Material included

A proposal to link the equation of state of a monocomponent hard-disk fluid to the equation of state of a polydisperse hard-disk mixture is presented. Event-driven molecular dynamics simulations are performed to obtain data for the compressibility factor of the monocomponent fluid and of 26 polydisperse mixtures with different size distributions. Those data are used to assess the proposal and to infer the values of the compressibility factor of the monocomponent hard-disk fluid in the metastable region from those of mixtures in the high-density region. The collapse of the curves for the different mixtures is excellent in the stable region. In the metastable regime, except for two mixtures in which crystallization is present, the outcome of the approach exhibits a rather good performance. The simulation results indicate that a (reduced) variance of the size distribution larger than about $0.01$ is sufficient to avoid crystallization and explore the metastable fluid branch., Comment: 12 pages, 8 figures; v3: new figures and new text added

Analytic approximations for the radial distribution function, the structure factor, and the equation of state of hard-core fluids in fractal dimension $d$ ($1 \leq d \leq 3$) are developed as heuristic interpolations from the knowledge of the exact and Percus-Yevick results for the hard-rod and hard-sphere fluids, respectively. In order to assess their value, such approximate results are compared with those of recent Monte Carlo simulations and numerical solutions of the Percus-Yevick equation for fractal dimension [M. Heinen et al., Phys. Rev. Lett. \textbf{115}, 097801 (2015)], a good agreement being observed., Comment: 10 pages, 7 figures; v2: new paragraph added at the end of the conclusion section

The relevance of neglecting three- and four-body interactions in the coarse-grained version of the Asakura-Oosawa model is examined. A mapping between the first few virial coefficients of the binary nonadditive hard-sphere mixture representative of this model and those arising from the coarse-grained (pairwise) depletion potential approximation allows for a quantitative evaluation of the effect of such interactions. This turns out to be especially important for large size ratios and large reservoir polymer packing fractions., Comment: 10 pages, 3 figures; v2: Results from free-volume theory included; Fig. 3 added, plus other minor changes

The problem of demixing in the Asakura-Oosawa colloid-polymer model is considered. The critical constants are computed using truncated virial expansions up to fifth order. While the exact analytical results for the second and third virial coefficients are known for any size ratio, analytical results for the fourth virial coefficient are provided here, and fifth virial coefficients are obtained numerically for particular size ratios using standard Monte Carlo techniques. We have computed the critical constants by successively considering the truncated virial series up to the second, third, fourth, and fifth virial coefficients. The results for the critical colloid and (reservoir) polymer packing fractions are compared with those that follow from available Monte Carlo simulations in the grand canonical ensemble. Limitations and perspectives of this approach are pointed out., Comment: 8 pages, 3 figures; v2: Inclusion of analytical expression for E11222 plus other minor changes; v3: Misprint in Eq. (2.20) corrected (see http://dx.doi.org/10.1063/1.4926462)

A recent proposal in which the equation of state of a polydisperse hard-sphere mixture is mapped onto that of the one-component fluid is extrapolated beyond the freezing point to estimate the jamming packing fraction $\phi_\text{J}$ of the polydisperse system as a simple function of $M_1M_3/M_2^2$, where $M_k$ is the $k$th moment of the size distribution. An analysis of experimental and simulation data of $\phi_\text{J}$ for a large number of different mixtures shows a remarkable general agreement with the theoretical estimate. To give extra support to the procedure, simulation data for seventeen mixtures in the high-density region are used to infer the equation of state of the pure hard-sphere system in the metastable region. An excellent collapse of the inferred curves up to the glass transition and a significant narrowing of the different out-of-equilibrium glass branches all the way to jamming are observed. Thus, the present approach provides an extremely simple criterion to unify in a common framework and to give coherence to data coming from very different polydisperse hard-sphere mixtures., Comment: 5 pages, 3 figures; v2: slight changes plus new references

The merits of different analytical equations of state for the hard-sphere system with respect to the recently computed high-accuracy value of the freezing-point packing fraction are assessed. It is found that the Carnahan-Starling-Kolafa and the branch-point approximant equations of state yield the best performance., Comment: 3 pages, 1 figure; v2: chemical potential added

The structural properties of fluids whose molecules interact via potentials with a hard core plus two piece-wise constant sections of different widths and heights are presented. These follow from the more general development previously introduced for potentials with a hard core plus $n$ piece-wise constant sections [Condens. Matter Phys. {\bf 15}, 23602 (2012)] in which use was made of a semi-analytic rational-function approximation method. The results of illustrative cases comprising eight different combinations of wells and shoulders are compared both with simulation data and with those that follow from the numerical solution of the Percus-Yevick and hypernetted-chain integral equations. It is found that the rational-function approximation generally predicts a more accurate radial distribution function than the Percus-Yevick theory and is comparable or even superior to the hypernetted-chain theory. This superiority over both integral equation theories is lost, however, at high densities, especially as the widths of the wells and/or the barriers increase., Comment: 10 pages, 11 figures; v2: Old Fig. 1 removed, new text on the correlation length, 7 new references added, plus other minor changes

The problem of demixing in a binary fluid mixture of highly asymmetric additive hard spheres is revisited. A comparison is presented between the results derived previously using truncated virial expansions for three finite size ratios with those that one obtains with the same approach in the extreme case in which one of the components consists of point particles. Since this latter system is known not to exhibit fluid-fluid segregation, the similarity observed for the behavior of the critical constants arising in the truncated series in all instances, while not being conclusive, may cast serious doubts as to the actual existence of a demixing fluid-fluid transition in disparate-sized binary additive hard-sphere mixtures., Comment: 3 pages, 1 figure

The fourth virial coefficient of asymmetric nonadditive binary mixtures of hard disks is computed with a standard Monte Carlo method. Wide ranges of size ratio ($0.05\leq q\leq 0.95$) and nonadditivity ($-0.5\leq \Delta\leq 0.5$) are covered. A comparison is made between the numerical results and those that follow from some theoretical developments. The possible use of these data in the derivation of new equations of state for these mixtures is illustrated by considering a rescaled virial expansion truncated to fourth order. The numerical results obtained using this equation of state are compared with Monte Carlo simulation data in the case of a size ratio $q=0.7$ and two nonadditivities $\Delta=\pm 0.2$., Comment: 9 pages, 7 figures; v2: section on equation of state added; tables moved to supplementary material (http://jcp.aip.org/resource/1/jcpsa6/v136/i18/p184505_s1#artObjSF)

A possible approximate route to obtain the equation of state of the monodisperse hard-sphere system in the metastable fluid region from the knowledge of the equation of state of a hard-sphere mixture at high densities is discussed. The proposal is illustrated by using recent Monte Carlo simulation data for the pressure of a binary mixture. It is further shown to exhibit high internal consistency., Comment: 4 pages, 2 figures; v2: Simulation data for one-component hard spheres included in Fig. 1

The question of whether the known virial coefficients are enough to determine the packing fraction $\eta_\infty$ at which the fluid equation of state of a hard-sphere fluid diverges is addressed. It is found that the information derived from the direct Pad\'e approximants to the compressibility factor constructed with the virial coefficients is inconclusive. An alternative approach is proposed which makes use of the same virial coefficients and of the equation of state in a form where the packing fraction is explicitly given as a function of the pressure. The results of this approach both for hard-disk and hard-sphere fluids, which can straightforwardly accommodate higher virial coefficients when available, lends support to the conjecture that $\eta_\infty$ is equal to the maximum packing fraction corresponding to an ordered crystalline structure., Comment: 10 pages, 6 figures; v2: discussion about hard-square and hard-hexagon systems on a lattice added; five new references

Different theoretical approaches for the thermodynamic properties and the equation of state for multicomponent mixtures of nonadditive hard spheres in $d$ dimensions are presented in a unified way. These include the theory by Hamad, our previous formulation, the original MIX1 theory, a recently proposed modified MIX1 theory, as well as a nonlinear extension of the MIX1 theory proposed in this paper. Explicit expressions for the compressibility factor, Helmholtz free energy, and second, third, and fourth virial coefficients are provided. A comparison is carried out with recent Monte Carlo data for the virial coefficients of asymmetric mixtures and with available simulation data for the compressibility factor, the critical consolute point, and the liquid-liquid coexistence curves. The merits and limitations of each theory are pointed out., Comment: 13 pages, 11 figures; v2: slight change of title, 2 new figures, new subsection on demixing added

Using the first seven known virial coefficients and forcing it to possess two branch-point singularities, a new equation of state for the hard-sphere fluid is proposed. This equation of state predicts accurate values of the higher virial coefficients, a radius of convergence smaller than the close-packing value, and it is as accurate as the rescaled virial expansion and better than the Pad\'e [3/3] equations of state. Consequences regarding the convergence properties of the virial series and the use of similar equations of state for hard-core fluids in $d$ dimensions are also pointed out., Comment: 6 pages, 4 tables, 3 figures; v2: enlarged version, extension to other dimensionalities; v3: typos in references corrected

A recently derived method [R. D. Rohrmann and A. Santos, Phys. Rev. E. {\bf 76}, 051202 (2007)] to obtain the exact solution of the Percus-Yevick equation for a fluid of hard spheres in (odd) $d$ dimensions is used to investigate the convergence properties of the resulting virial series. This is done both for the virial and compressibility routes, in which the virial coefficients $B_j$ are expressed in terms of the solution of a set of $(d-1)/2$ coupled algebraic equations which become nonlinear for $d \geq 5$. Results have been derived up to $d=13$. A confirmation of the alternating character of the series for $d\geq 5$, due to the existence of a branch point on the negative real axis, is found and the radius of convergence is explicitly determined for each dimension. The resulting scaled density per dimension $2 \eta^{1/d}$, where $\eta$ is the packing fraction, is wholly consistent with the limiting value of 1 for $d \to \infty$. Finally, the values for $B_j$ predicted by the virial and compressibility routes in the Percus-Yevick approximation are compared with the known exact values [N. Clisby and B. M. McCoy, J. Stat. Phys. {\bf 122}, 15 (2006)], Comment: 9 pages, 6 figures

The depletion force and depletion potential between two in principle unequal "big" hard spheres embedded in a multicomponent mixture of "small" hard spheres are computed using the Rational Function Approximation method for the structural properties of hard-sphere mixtures [S. B. Yuste, A. Santos, and M. L\'opez de Haro, J. Chem. Phys. {\bf 108}, 3683 (1998)]. The cases of equal solute particles and of one big particle and a hard planar wall in a background monodisperse hard-sphere fluid are explicitly analyzed. An improvement over the performance of the Percus-Yevick theory and good agreement with available simulation results are found, Comment: 10 pages, 5 figures; v2: few minor additions and reduction in the number of figures; v3: Fig. 2 corrected (see http://dx.doi.org/10.1063/1.4874639)

The rational function approximation method, density functional theory, and NVT Monte Carlo simulation are used to obtain the density profiles of multicomponent hard-sphere mixtures near a planar hard wall. Binary mixtures with a size ratio 1:3 in which both components occupy a similar volume are specifically examined. The results indicate that the present version of density functional theory yields an excellent overall performance. A reasonably accurate behavior of the rational function approximation method is also observed, except in the vicinity of the first minimum, where it may even predict unphysical negative values., Comment: 10 pages, 5 figures; v2: minor changes; Fig. 5 is new; to be published in PRE

The direct correlation function and the (static) structure factor for a seven-dimensional hard-sphere fluid are considered. Analytical results for these quantities are derived within the Percus-Yevick theory, Comment: 3 pages, 2 tables, 1 figure; v2: minor changes; to be published in JCP

Recent Monte Carlo simulation results for the contact values of polydisperse hard-sphere mixtures at a hard planar wall are considered in the light of a universality assumption made in approximate theoretical approaches. It is found that the data seem to fulfill the universality ansatz reasonably well, thus opening up the possibility of inferring properties of complicated systems from the study of simpler ones, Comment: 9 pages, 2 figures; v2: minor changes; to be published in the special issue of Molecular Physics dedicated to the Seventh Liblice Conference on the Statistical Mechanics of Liquids (Lednice, Czech Republic, June 11-16, 2006)

Monte Carlo simulations on the structural properties of ternary fluid mixtures of additive hard spheres are reported. The results are compared with those obtained from a recent analytical approximation [S. B. Yuste, A. Santos, and M. Lopez de Haro, J. Chem. Phys. 108, 3683 (1998)] to the radial distribution functions of hard-sphere mixtures and with the results derived from the solution of the Ornstein-Zernike integral equation with both the Martynov-Sarkisov and the Percus-Yevick closures. Very good agreement between the results of the first two approaches and simulation is observed, with a noticeable improvement over the Percus-Yevick predictions especially near contact., Comment: 11 pages, including 8 figures; A minor change; accepted for publication in PRE