arXiv subjects

Santos B. Yuste

Publications and source records attributed to Santos B. Yuste.

At least 19 recordsLinked to original sources

arXiv2025

Discontinuous Structural Transitions in Fluids with Competing Interactions

This paper explores how competing interactions in the intermolecular potential of fluids affect their structural transitions. This 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.

cond-mat.soft↗

arXiv2024

On a conjecture concerning the Fisher--Widom line and the line of vanishing excess isothermal compressibility in simple fluids

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.

cond-mat.soft↗

arXiv2022

Structural and thermodynamic properties of fluids whose molecules interact via one-, two-, and three-step potentials

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.

cond-mat.soft↗

arXiv2021

Structural properties of additive binary hard-sphere mixtures. III. Direct correlation functions

An analysis of the direct correlation functions $c_{ij} (r)$ of binary additive hard-sphere mixtures of diameters $σ_s$ and $σ_b$ (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 $c_{ss}(r<σ_s)$ and $c_{bb}(r<σ_b)$ in both approaches are monotonic and can be well represented by a low-order polynomial, while the function $c_{sb}(r<\frac{1}{2}(σ_b+σ_s))$ is not monotonic and exhibits a well defined minimum near $r=\frac{1}{2}(σ_b-σ_s)$, whose properties are studied in detail. Additionally, we show that the second derivative $c_{sb}''(r)$ presents a jump discontinuity at $r=\frac{1}{2}(σ_b-σ_s)$ whose magnitude satisfies the same relationship with the contact values of the radial distribution function as in the Percus-Yevick theory.

cond-mat.soft↗

arXiv2021

Structural properties of additive binary hard-sphere mixtures. II. Asymptotic behavior and structural crossovers

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.

cond-mat.soft↗

arXiv2020

Structural and Thermodynamic Properties of Hard-Sphere Fluids

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.

cond-mat.soft↗

arXiv2020

Equation of State of Four- and Five-Dimensional Hard-Hypersphere Mixtures

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

cond-mat.soft↗

arXiv2018

Structural properties of the Jagla fluid

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.

cond-mat.soft↗

arXiv2017

Equation of state of polydisperse hard-disk mixtures in the high-density regime

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.

cond-mat.soft↗

arXiv2017

Virial coefficients, equation of state, and demixing of binary asymmetric nonadditive hard-disk mixtures

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 $Δ=0.3$), 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.

cond-mat.soft↗

arXiv2015

Virial coefficients and demixing in the Asakura-Oosawa model

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.

cond-mat.soft↗

arXiv2014

A simple effective rule to estimate the jamming packing fraction of polydisperse hard spheres

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 $ϕ_\text{J}$ 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 $ϕ_\text{J}$ 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.

cond-mat.stat-mech↗

arXiv2014

Fast, Accurate and Robust Adaptive Finite Difference Methods for Fractional Diffusion Equations: The Size of the Timesteps does Matter

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.

math.NA↗

arXiv2013

A Finite Difference Method with Non-uniform Timesteps for Fractional Diffusion Equations

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.

math.NA↗

arXiv2013

Structural properties of fluids interacting via piece-wise constant potentials with a hard core

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.

cond-mat.soft↗

arXiv2013

Arrival statistics and exploration properties of mortal walkers

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.

cond-mat.stat-mech↗

arXiv2012

Fourth virial coefficients of asymmetric nonadditive hard-disc mixtures

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 ($-0.5\leq Δ\leq 0.5$) 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 $Δ=\pm 0.2$.

cond-mat.soft↗

arXiv2011

Communication: Inferring the equation of state of a metastable hard-sphere fluid from the equation of state of a hard-sphere mixture at high densities

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.

cond-mat.soft↗