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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

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

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

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)

The computation time required by standard finite difference methods with fixed timesteps for solving fractional diffusion equations is usually very large because the number of operations required to find the solution scales as the square of the number of timesteps. Besides, the solutions of these problems usually involve markedly different time scales, which leads to quite inhomogeneous numerical errors. A natural way to address these difficulties is by resorting to adaptive numerical methods where the size of the timesteps is chosen according to the behaviour of the solution. A key feature of these methods is then the efficiency of the adaptive algorithm employed to dynamically set the size of every timestep. Here we discuss two adaptive methods based on the step-doubling technique. These methods are, in many cases, immensely faster than the corresponding standard method with fixed timesteps and they allow a tolerance level to be set for the numerical errors that turns out to be a good indicator of the actual errors.

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

We study some of the salient features of the arrival statistics and exploration properties of mortal random walkers, that is, walkers that may die as they move, or as they wait to move. Such evanescence or death events have profound consequences for quantities such as the number of distinct sites visited which are relevant for the computation of encounter-controlled rates in chemical kinetics. We exploit the observation that well-known methods developed decades ago for immortal walkers are widely applicable to mortal walkers. The particular cases of exponential and power-law evanescence are considered in detail. Finally, we discuss the relevance of our results to the target problem with mortal traps and a particular application thereof, namely, the defect diffusion model. Evanescence of defects is postulated as a possible complementary contribution or perhaps even an alternative to anomalous diffusion to explain observed stretched exponential relaxation behavior.

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 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)

An implicit finite difference method with non-uniform timesteps for solving the fractional diffusion equation in the Caputo form is proposed. The method allows one to build adaptive methods where the size of the timesteps is adjusted to the behaviour of the solution in order to keep the numerical errors small without the penalty of a huge computational cost. The method is unconditionally stable and convergent. In fact, it is shown that consistency and stability implies convergence for a rather general class of fractional finite difference methods to which the present method belongs. The huge computational advantage of adaptive methods against fixed step methods for fractional diffusion equations is illustrated by solving the problem of the dispersion of a flux of subdiffusive particles stemming from a point source., Comment: This version correct some mistakes of the published version: superindex n-1 should be 0 in Eqs. (27), (28), (30) and (33), superindex m in the second line below Eq. (34) should be n; Eq.(34) is incorrect and must be removed; the reference to this equation in Sect. 4 must be changed to Eq. (33). The main results and conclusions of the paper are not affected by these corrections

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

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

The two-body interaction in dilute solutions of polymer chains in good solvents can be modeled by means of effective bounded potentials, the simplest of which being that of penetrable spheres (PSs). In this paper we construct two simple analytical theories for the structural properties of PS fluids: a low-temperature (LT) approximation, that can be seen as an extension to PSs of the well-known solution of the Percus-Yevick (PY) equation for hard spheres, and a high-temperature (HT) approximation based on the exact asymptotic behavior in the limit of infinite temperature. Monte Carlo simulations for a wide range of temperatures and densities are performed to assess the validity of both theories. It is found that, despite their simplicity, the HT and LT approximations exhibit a fair agreement with the simulation data within their respective domains of applicability, so that they complement each other. A comparison with numerical solutions of the PY and the hypernetted-chain approximations is also carried out, the latter showing a very good performance, except inside the core at low temperatures., Comment: 14 pages, 8 figures; v2: some figures redone; small changes

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

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)

The aim of this work is to investigate to what extent the structural properties of a short-range square-well (SW) fluid of range $\lambda$ at a given packing fraction and reduced temperature can be represented by those of a sticky-hard-sphere (SHS) fluid at the same packing fraction and an effective stickiness parameter $\tau$. Such an equivalence cannot hold for the radial distribution function since this function has a delta singularity at contact in the SHS case, while it has a jump discontinuity at $r=\lambda$ in the SW case. Therefore, the equivalence is explored with the cavity function $y(r)$. Optimization of the agreement between $y_{\sw}$ and $y_{\shs}$ to first order in density suggests the choice for $\tau$. We have performed Monte Carlo (MC) simulations of the SW fluid for $\lambda=1.05$, 1.02, and 1.01 at several densities and temperatures $T^*$ such that $\tau=0.13$, 0.2, and 0.5. The resulting cavity functions have been compared with MC data of SHS fluids obtained by Miller and Frenkel [J. Phys: Cond. Matter 16, S4901 (2004)]. Although, at given values of $\eta$ and $\tau$, some local discrepancies between $y_{\sw}$ and $y_{\shs}$ exist (especially for $\lambda=1.05$), the SW data converge smoothly toward the SHS values as $\lambda-1$ decreases. The approximate mapping $y_{\sw}\to y_{\shs}$ is exploited to estimate the internal energy and structure factor of the SW fluid from those of the SHS fluid. Taking for $y_{\shs}$ the solution of the Percus--Yevick equation as well as the rational-function approximation, the radial distribution function $g(r)$ of the SW fluid is theoretically estimated and a good agreement with our MC simulations is found. Finally, a similar study is carried out for short-range SW fluid mixtures., Comment: 14 pages, including 3 tables and 14 figures; v2: typo in Eq. (5.1) corrected, Fig. 14 redone, to be published in JCP

We study the reaction front for the process $A+B\to C$ in which the reagents move subdiffusively. We propose a fractional reaction-subdiffusion equation in which both the motion and the reaction terms are affected by the subdiffusive character of the process. Scaling solutions to these equations are presented and compared with those of a direct numerical integration of the equations. We find that for reactants whose mean square displacement varies sublinearly with time as $ \sim t^\gamma$, the scaling behaviors of the reaction front can be recovered from those of the corresponding diffusive problem with the substitution $t\to t^\gamma$, Comment: Errata corrected, one reference updated

Weighted averaged finite difference methods for solving fractional diffusion equations are discussed and different formulae of the discretization of the Riemann-Liouville derivative are considered. The stability analysis of the different numerical schemes is carried out by means of a procedure close to the well-known von Neumann method of ordinary diffusion equations. The stability bounds are easily found and checked in some representative examples., Comment: Communication presented at the FDA'04 Workshop (with some minor corrections and updates)

We study the average shape of fluctuations for subdiffusive processes, i.e., processes with uncorrelated increments but where the waiting time distribution has a broad power-law tail. This shape is obtained analytically by means of a fractional diffusion approach. We find that, in contrast with processes where the waiting time between increments has finite variance, the fluctuation shape is no longer a semicircle: it tends to adopt a table-like form as the subdiffusive character of the process increases. The theoretical predictions are compared with numerical simulation results., Comment: 4 pages, 6 figures. Accepted for publication Phys. Rev. E (Replaced for the latest version, in press.) Section II rewritten

An overview is presented of recent work on some statistical problems on multiparticle random walks. We consider a Euclidean, deterministic fractal or disordered lattice and N >> 1 independent random walkers initially (t=0) placed onto the same site of the substrate. Three classes of problems are considered: (i) the evaluation of the average number of distinct sites visited (territory explored) up to time t by the N random walkers, (ii) the statistical description of the first passage time t_{j,N} to a given distance of the first j random walkers (order statistics of exit times), and (iii) the statistical description of the time \mathbf{t}_{j,N} elapsed until the first j random walkers are trapped when a Euclidean lattice is randomly occupied by a concentration c of traps (order statistics of the trapping problem). Although these problems are very different in nature, their solutions share the same form of a series in ln^{-n}(N) \ln^m \ln (N) (with n>=1 and 0<=m<=n) for N>>1. These corrective terms contribute substantially to the statistical quantities even for relatively large values of N., Comment: 14 pages, 13 figures, RevTex 4

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

When a large number N of independent diffusing particles are placed upon a site of a d-dimensional Euclidean lattice randomly occupied by a concentration c of traps, what is the m-th moment of the time t_{j,N} elapsed until the first j are trapped? An exact answer is given in terms of the probability Phi_M(t) that no particle of an initial set of M=N, N-1,..., N-j particles is trapped by time t. The Rosenstock approximation is used to evaluate Phi_M(t), and it is found that for a large range of trap concentracions the m-th moment of t_{j,N} goes as x^{-m} and its variance as x^{-2}, x being ln^{2/d} (1-c) ln N. A rigorous asymptotic expression (dominant and two corrective terms) is given for for the one-dimensional lattice., Comment: 11 pages, 7 figures, to be published in Phys. Rev. E