arXiv subjects

James W. Dufty

Publications and source records attributed to James W. Dufty.

At least 19 recordsLinked to original sources

arXiv2017

Nonempirical Semi-local Free-Energy Density Functional for Matter Under Extreme Conditions

Realizing the potential for predictive density functional calculations of matter under extreme conditions depends crucially upon having an exchange-correlation (XC) free energy functional accurate over a wide range of state conditions. Unlike the ground-state case, no such functional exists. We remedy that with systematic construction of a generalized gradient approximation XC free-energy functional based on rigorous constraints, including the free energy gradient expansion. The new functional provides the correct temperature dependence in the slowly varying regime and the correct zero-T, high-T, and homogeneous electron gas limits. Its accuracy in the warm dense matter regime is attested by excellent agreement of the calculated deuterium equation of state with reference path integral Monte Carlo results at intermediate and elevated T. Pressure shifts for hot electrons in compressed static fcc Al and for low density Al demonstrate the combined magnitude of thermal and gradient effects handled well by this functional over a wide T range.

cond-mat.mtrl-sci↗

arXiv2017

Density Functional Theory for the Electron Gas and for Jellium

Density Functional Theory relies on universal functionals characteristic of a given system. Those functionals in general are different for the electron gas and for jellium (electron gas with uniform background). However, jellium is frequently used to construct approximate functionals for the electron gas (e.g., local density approximation, gradient expansions). The precise relationship of the exact functionals for the two systems is addressed here. In particular, it is shown that the exchange - correlation functionals for the inhomogeneous electron gas and inhomogeneous jellium are the same. This justifies theoretical and quantum Monte Carlo simulation studies of jellium to guide the construction of functionals for the electron gas. Related issues of the thermodynamic limit are noted as well.

cond-mat.stat-mech↗

arXiv2016

Finite Temperature Scaling in Density Functional Theory

A previous analysis of scaling, bounds, and inequalities for the non-interacting functionals of thermal density functional theory is extended to the full interacting functionals. The results are obtained from analysis of the related functionals from the equilibrium statistical mechanics of thermodynamics for an inhomogeneous system. Their extension to the functionals of density functional theory is described.

cond-mat.stat-mech↗

arXiv2016

Revised Thomas-Fermi Approximation for Singular Potentials

Approximations to the many-fermion free energy density functional that include the Thomas-Fermi (TF) form for the non-interacting part lead to singular densities for singular external potentials (e.g. attractive Coulomb). This limitation of the TF approximation is addressed here by a formal map of the exact Euler equation for the density onto an equivalent TF form characterized by a modified Kohn-Sham potential. It is shown to be a "regularized" version of the Kohn-Sham potential, tempered by convolution with a finite-temperature response function. The resulting density is non-singular, with the equilibrium properties obtained from the total free energy functional evaluated at this density. This new representation is formally exact. Approximate expressions for the regularized potential are given to leading order in a non-locality parameter and the limiting behavior at high and low temperatures is described. The non-interacting part of the free energy in this approximation is the usual Thomas-Fermi functional. These results generalize and extend to finite temperatures the ground-state regularization by Parr and Ghosh (Proc. Nat. Acad. Sci. 83, 3577 (1986)) and by Pratt, Hoffman, and Harris (J. Chem. Phys. 92, 1818 (1988)) and formally systematize the finite-temperature regularization given by the latter authors.

cond-mat.stat-mech↗

arXiv2011

Thermal segregation of intruders in the Fourier state of a granular gas

A low density binary mixture of granular gases is considered within the Boltzmann kinetic theory. One component, the intruders, is taken to be dilute with respect to the other, and thermal segregation of the two species is described for a special exact solution to the Boltzmann equation. This solution has a macroscopic hydrodynamic representation with a constant temperature gradient and is referred to as the Fourier state. The thermal diffusion factor characterizing conditions for segregation is calculated without the usual restriction to Navier-Stokes hydrodynamics. Molecular dynamics simulations are reported for comparison with the results for this idealized Fourier state.

cond-mat.stat-mech↗

arXiv2011

Classical Representation of a Quantum System at Equilibrium

A quantum system at equilibrium is represented by a corresponding classical system, chosen to reproduce the thermodynamic and structural properties. The objective is to develop a means for exploiting strong coupling classical methods (e.g., MD, integral equations, DFT) to describe quantum systems. The classical system has an effective temperature, local chemical potential, and pair interaction that are defined by requiring equivalence of the grand potential and its functional derivatives with respect to the external and pair potentials for the classical and quantum systems. Practical inversion of this mapping for the classical properties is effected via the hypernetted chain approximation, leading to representations as functionals of the quantum pair correlation function. As an illustration, the parameters of the classical system are determined approximately such that ideal gas and weak coupling RPA limits are preserved.

cond-mat.stat-mech↗

arXiv2011

Finite Temperature Scaling, Bounds, and Inequalities for the Non-interacting Density Functionals

Finite temperature density functional theory requires representations for the internal energy, entropy, and free energy as functionals of the local density field. A central formal difficulty for an orbital-free representation is construction of the corresponding functionals for non-interacting particles in an arbitrary external potential. That problem is posed here in the context of the equilibrium statistical mechanics of an inhomogeneous system. The density functionals are defined and shown to be equal to the extremal state for a functional of the reduced one-particle statistical operators. Convexity of the latter functionals implies a class of general inequalities. First, it is shown that the familiar von Weizsäcker lower bound for zero temperature functionals applies at finite temperature as well. An upper bound is obtained in terms of a single-particle statistical operator corresponding to the Thomas-Fermi approximation. Next, the behavior of the density functionals under coordinate scaling is obtained. The inequalities are exploited to obtain a class of upper and lower bounds at constant temperature, and a complementary class at constant density. The utility of such constraints and their relationship to corresponding results at zero temperature are discussed.

cond-mat.stat-mech↗

arXiv2011

Choosing Hydrodynamic fields

Continuum mechanics (e.g., hydrodynamics, elasticity theory) is based on the assumption that a small set of fields provides a closed description on large space and time scales. Conditions governing the choice for these fields are discussed in the context of granular fluids and multi-component fluids. In the first case, the relevance of temperature or energy as a hydrodynamic field is justified. For mixtures, the use of a total temperature and single flow velocity is compared with the use of multiple species temperatures and velocities.

cond-mat.stat-mech↗

arXiv2011

Thermal Segregation Beyond Navier-Stokes

A dilute suspension of impurities in a low density gas is described by the Boltzmann and Boltzman-Lorentz kinetic theory. Scaling forms for the species distribution functions allow an exact determination of the hydrodynamic fields, without restriction to small thermal gradients or Navier-Stokes hydrodynamics. The thermal diffusion factor characterizing sedimentation is identified in terms of collision integrals as functions of the mechanical properties of the particles and the temperature gradient. An evaluation of the collision integrals using Sonine polynomial approximations is discussed. Conditions for segregation both along and opposite the temperature gradient are found, in contrast to the Navier-Stokes description for which no segregation occurs.

cond-mat.stat-mech↗

arXiv2009

Response Functions for a Granular Fluid

The response of an isolated granular fluid to small perturbations of the hydrodynamic fields is considered. The corresponding linear response functions are identified in terms of a formal solution to the Liouville equation including the effects of the cooling reference state. These functions are evaluated exactly in the asymptotic long wavelength limit and shown to represent hydrodynamic modes. More generally, the linear granular Navier-Stokes equations for the response functions and related Langevin equations are obtained from an extension of Mori's identity. The resulting Green-Kubo expressions for transport coefficients are compared and contrasted with those for a molecular fluid. Next the response functions are described in terms of an effective dynamics in the single particle phase space. A closed linear kinetic equation is obtained formally in terms of a linear two particle functional. This closure is evaluated for two examples: a short time Markovian approximation, and a low density expansion on length and time scales of the mean free time and mean free path. The former is a generalization of the revised Enskog kinetic theory to include velocity correlations. The latter is an extension of the Boltzmann equation to include the effects of recollisions (rings) among the particles.

cond-mat.stat-mech↗

arXiv2009

Hydrodynamic equations for a granular mixture from kinetic theory - fundamental considerations

In this review, a theoretical description is provided for the solid (granular) phase of the gas-solid flows that are the focus of this book. Emphasis is placed on the fundamental concepts involved in deriving a macroscopic hydrodynamic description for the granular material in terms of the hydrodynamic fields (species densities, flow velocity, and the granular temperature) from a prescribed "microscopic" interaction among the grains. To this end, the role of the interstitial gas phase, body forces such as gravity, and other coupling to the environment are suppressed and retained only via a possible non-conservative external force and implicit boundary conditions. The general notion of a kinetic equation is introduced to obtain macroscopic balance equations for the fields. Constitutive equations for the fluxes in these balance equations are obtained from special "normal" solutions to the kinetic equation, resulting in a closed set of hydrodynamic equations. This general constructive procedure is illustrated for the Boltzmann-Enskog kinetic equation describing a system of smooth, inelastic hard spheres. For weakly inhomogeneous fluid states the granular Navier-Stokes hydrodynamic equations are obtained, including exact integral equations for the transport coefficients. A method to obtain practical solutions to these integral equations is described. Finally, a brief discussion is given for hydrodynamics beyond the Navier-Stokes limitations.

cond-mat.stat-mech↗

arXiv2008

Kinetic Theory for Electron Dynamics Near a Positive Ion

A theoretical description of time correlation functions for electron properties in the presence of a positive ion of charge number Z is given. The simplest case of an electron gas distorted by a single ion is considered. A semi-classical representation with a regularized electron - ion potential is used to obtain a linear kinetic theory that is asymptotically exact at short times. This Markovian approximation includes all initial (equilibrium) electron - electron and electron - ion correlations through renormalized pair potentials. The kinetic theory is solved in terms of single particle trajectories of the electron - ion potential and a dielectric function for the inhomogeneous electron gas. The results are illustrated by a calculation of the autocorrelation function for the electron field at the ion. The dependence on charge number Z is shown to be dominated by the bound states of the effective electron - ion potential. On this basis, a very simple practical representation of the trajectories is proposed and shown to be accurate over a wide range including strong electron - ion coupling. This simple representation is then used for a brief analysis of the dielectric function for the inhomogeneous electron gas.

cond-mat.stat-mech↗

arXiv2007

Granular Fluids

The terminology granular matter refers to systems with a large number of hard objects (grains) of mesoscopic size ranging from millimeters to meters. Geological examples include desert sand and the rocks of a landslide. But the scope of such systems is much broader, including powders and snow, edible products such a seeds and salt, medical products like pills, and extraterrestrial systems such as the surface regolith of Mars and the rings of Saturn. The importance of a fundamental understanding for granular matter properties can hardly be overestimated. Practical issues of current concern range from disaster mitigation of avalanches and explosions of grain silos to immense economic consequences within the pharmaceutical industry. In addition, they are of academic and conceptual importance as well as examples of systems far from equilibrium. Under many conditions of interest, granular matter flows like a normal fluid. In the latter case such flows are accurately described by the equations of hydrodynamics. Attention is focused here on the possibility for a corresponding hydrodynamic description of granular flows. The tools of nonequilibrium statistical mechanics, developed over the past fifty years for fluids composed of atoms and molecules, are applied here to a system of grains for a fundamental approach to both qualitative questions and practical quantitative predictions. The nonlinear Navier-Stokes equations and expressions for the associated transport coefficients are obtained.

cond-mat.stat-mech↗

arXiv2007

Kinetic Theory of Response Functions for the Hard Sphere Granular Fluid

The response functions for small spatial perturbations of a homogeneous granular fluid have been described recently. In appropriate dimensionless variables, they have the form of stationary state time correlation functions. Here, these functions are expressed in terms of reduced single particle functions that are expected to obey a linear kinetic equation. The functional assumption required for such a kinetic equation, and a Markov approximation for its implementation are discussed. If, in addition, static velocity correlations are neglected, a granular fluid version of the linearized Enskog kinetic theory is obtained. The derivation makes no a priori limitation on the density, space and time scale, nor degree of inelasticity. As an illustration, recently derived Helfand and Green-Kubo expressions for the Navier-Stokes order transport coefficients are evaluated with this kinetic theory. The results are in agreement with those obtained from the Chapman-Enskog solution to the nonlinear Enskog kinetic equation.

cond-mat.soft↗

arXiv2007

Nonequilibrium Statistical Mechanics and Hydrodynamics for a Granular Fluid

Granular fluids consist of collections of activated mesoscopic or macroscopic particles (e.g., powders or grains) whose flows often appear similar to those of normal fluids. To explore the qualitative and quantitative description of these flows an idealized model for such fluids, a system of smooth inelastic hard spheres, is considered. The single feature distinguishing granular and normal fluids being explored in this way is the inelasticity of collisions. The dominant differences observed in real granular fluids are indeed captured by this feature. Following a brief introductory description of real granular fluids and motivation for the idealized model, the elements of nonequilibrium statistical mechanics are recalled (observables, states, and their dynamics). Peculiarities of the hard sphere interactions are developed in detail. The exact microscopic balance equations for the number, energy, and momentum densities are derived and their averages described as the origin for a possible macroscopic continuum mechanics description. This formally exact analysis leads to closed, macroscopic hydrodynamic equations through the notion of a "normal" state. This concept is introduced and the Navier-Stokes constitutive equations are derived, with associated Green-Kubo expressions for the transport coefficients. A parallel description of granular gases is described in the context of kinetic theory, and the Boltzmann limit is identified critically. The construction of the "normal" solution to the kinetic equation is outlined, and Navier-Stokes order hydrodynamic equations are re-derived for a low density granular gas.

cond-mat.stat-mech↗

arXiv2007

Fourier's Law for a Granular Fluid

Newton' viscosity law for the momentum flux and Fourier's law for the heat flux define Navier-Stokes hydrodynamics for a simple, one component fluid. There is ample evidence that a hydrodynamic description applies as well to a mesoscopic granular fluid with the same form for Newton's viscosity law. However, theory predicts a qualitative difference for Fourier's law with an additional contribution from density gradients even at uniform temperature. The reasons for the absence of such terms for normal fluids are indicated, and a related microscopic explanation for their existence in granular fluids is presented.

cond-mat.stat-mech↗

arXiv2006

Linear Response and Hydrodynamics for Granular Fluids

A formal derivation of linear hydrodynamics for a granular fluid is given. The linear response to small spatial perturbations of the homogeneous reference state is studied in detail using methods of non-equilibrium statistical mechanics. A transport matrix for macroscopic excitations in the fluid is defined in terms of the response functions. An expansion in the wavevector to second order allows identification of all phenomenological susceptibilities and transport coefficients through Navier-Stokes order, in terms of appropriate time correlation functions. The transport coefficients in this representation are the generalization to granular fluids of the familiar Helfand and Green-Kubo relations for normal fluids. The analysis applies to a wide range of collision rules. Important differences in both the analysis and results from those for normal fluids are identified and discussed. A scaling limit is described corresponding to the conditions under which idealized inelastic hard sphere models can apply. Further details and interpretation are provided in the paper following this one, by specialization to the case of smooth, inelastic hard spheres with constant coefficient of restitution.

cond-mat.stat-mech↗

arXiv2006

Transport Coefficients for the Hard Sphere Granular Fluid

In the preceding paper, linear response methods have been applied to obtain formally exact expressions for the parameters of Navier-Stokes order hydrodynamics. The analysis there is general, applying to both normal and granular fluids with a wide range of collision rules. Those results are specialized here to the case of smooth, inelastic hard spheres with constant coefficient of normal restitution, for further elaboration. Explicit expressions for the cooling rate, pressure, and the transport coefficients are given and compared with the corresponding expressions for a system of elastic hard spheres. The scope of the results for further analytical explorations and possible numerical evaluation is discussed.

cond-mat.stat-mech↗