Previously, it has been shown that the direct correlation function for a Lennard-Jones fluid could be modeled by a sum of that for hard-spheres, a mean-field tail and a simple linear correction in the core region constructed so as to reproduce the (known) bulk equation of state of the fluid(Lutsko, JCP 127, 054701 (2007)). Here, this model is combined with ideas from Fundamental Measure Theory to construct a density functional theory for the free energy. The theory is shown to accurately describe a range of inhomogeneous conditions including the liquid-vapor interface, the fluid in contact with a hard wall and a fluid confined in a slit pore. The theory gives quantitatively accurate predictions for the surface tension, including its dependence on the potential cutoff. It also obeys two important exact conditions: that relating the direct correlation function to the functional derivative of the free energy with respect to density, and the wall theorem.
The process of nucleation of vapor bubbles from a superheated liquid and of liquid droplets from a supersaturated vapor is investigated using the Modified-Core van der Waals model Density Functional Theory (Lutsko, JCP 128, 184711 (2008)). A novel approach is developed whereby nucleation is viewed as a transition from a metastable state to a stable state via the minimum free energy path which is identified using the nudged elastic-band method for exploring free energy surfaces. This allows for the unbiased calculation of the properties of sub- and super-critical clusters, as well as of the cri…
A simple model is proposed for the direct correlation function (DCF) for simple fluids consisting of a hard-core contribution, a simple parametrized core correction, and a mean-field tail. The model requires as input only the free energy of the homogeneous fluid, obtained, e.g., from thermodynamic perturbation theory. Comparison to the DCF obtained from simulation of a Lennard-Jones fluid shows this to be a surprisingly good approximation for a wide range of densities. The model is used to construct a density functional theory for inhomogeneous fluids which is applied to the problem of calcula…
We extend Mode-Coupling Theory (MCT) to inhomogeneous situations, relevant for supercooled liquid in pores, close to a surface, or in an external field. We compute the response of the dynamical structure factor to a static inhomogeneous external potential and provide the first direct evidence that the standard formulation of MCT is associated with a diverging length scale. We find in particular that the so called ``cages'' are in fact extended objects. Although close to the transition the dynamic length grows as |T-T_c|^-1/4 in _both_ the beta and alpha regimes, our results suggest that the fr…
Classical density functional theory (DFT) is a statistical mechanical theory for calculating the density profiles of the molecules in a liquid. It is widely used, for example. to calculate the density distribution of the molecules in the vicinity of a confining wall, the interfacial tension, the wetting behaviour and many other properties of nonuniform liquids. DFT can however be somewhat daunting to students entering the field, because of the many connections to other areas of liquid-state science that are required and used to develop the theories. Here we give an introduction to some of the …
At high densities fluids of strongly dipolar spherical particles exhibit spontaneous long-ranged orientational order. Typically, due to demagnetization effects induced by the long range of the dipolar interactions, the magnetization structure is spatially inhomogeneous and depends on the shape of the sample. We determine this structure for a cubic sample by the free minimization of an appropriate microscopic density functional using simulated annealing. We find a vortex structure resembling four domains separated by four domain walls whose thickness increases proportional to the system size L.…
We show that one may view the self and the distinct part of the van Hove dynamic correlation function of a simple fluid as the one-body density distributions of a binary mixture that evolve in time according to dynamical density functional theory. For a test case of soft core Brownian particles the theory yields results for the van Hove function that agree quantitatively with those of our Brownian dynamics computer simulations. At sufficiently high densities the free energy landscape underlying the dynamics exhibits a barrier as a function of the mean particle displacement, shedding new light …
We propose microscopic density functional theory for inhomogeneous star polymers. Our approach is based on fundamental measure theory for hard spheres, and on Wertheim's first- and second-order perturbation theory for the interparticle connectivity. For simplicity we consider a model in which all the arms are of the same length, but our approach can be easily extended to the case of stars with arms of arbitrary lengths.
The search for local structures within a disordered medium has led to proposals of several methods for probing transient short-range symmetry in a homogeneous mono-atomic liquid. We offer a comparison of different characterizations of such local structure in an in-homogeneous liquid. We simulate the interfaces between a Lennard-Jones liquid and (i) a flat Lennard-Jones wall, (ii) a wall of face-centered cubic-packed Lennard-Jones particles, and (iii) a Lennard-Jones vapor. The interface density distributions in cases (i) and (ii) have oscillations extending several particle diameters into the …
The Squared-Gradient approximation to the Modified-Core Van der Waals density functional theory model is developed. A simple, explicit expression for the SGA coefficient involving only the bulk equation of state and the interaction potential is given. The model is solved for planar interfaces and spherical clusters and is shown to be quantitatively accurate in comparisons to computer simulations. An approximate technique for solving the SGA based on piecewise-linear density profiles is introduced and is shown to give reasonable zeroth-order approximations to the numerical solution of the model…
Based on a microscopic density functional theory we calculate the internal structure of the three-phase contact line between liquid, vapor, and a confining wall as well as the morphology of liquid wetting films on a substrate exhibiting a chemical step. We present a refined numerical analysis of the nonlocal density functional which describes the interface morphologies and the corresponding line tensions. These results are compared with those predicted by a more simple phenomenological interface displacement model. Except for the case that the interface exhibits large curvatures, we find that …
We develop a general framework to compute the scaling of entanglement entropy in inhomogeneous one-dimensional quantum systems belonging to the Luttinger liquid universality class. While much insight has been gained in homogeneous systems by making use of conformal field theory techniques, our focus is on systems for which the Luttinger parameter $K$ depends on position, and conformal invariance is broken. An important point of our analysis is that contributions stemming from the UV cutoff have to be treated very carefully, since they now depend on position. We show that such terms can be remo…
The theory of quasi-neutral equilibrium states of charges above liquid dielectric surface is built. This theory is based on first principles of quantum statistics for systems, comprising many identical particles. The proposed approach is concerned with applying the variation principle, modified for the considered systems, and the Thomas-Fermi model. In terms of the developed theory a self-consistency equations are obtained. These equations provide the relation between the main parameters, describing the system: the potential of static electric field, the distribution function of charges and th…
Tomonaga-Luttinger liquids (TLLs) can be used to effectively describe one-dimensional quantum many-body systems such as ultracold atoms, charges in nanowires, superconducting circuits, and gapless spin chains. Their properties are given by two parameters, the propagation velocity and the Luttinger parameter. Here we study inhomogeneous TLLs where these are promoted to functions of position and demonstrate that they profoundly affect the dynamics: In general, besides curving the light cone, we show that propagation is no longer ballistically localized to the light-cone trajectories, different f…
Using the adiabatic connection, we formulate the free energy in terms of the correlation function of a fictitious system, $h_λ({\bf r},{\bf r}')$, where $λ$ determines the interaction strength. To obtain $h_λ({\bf r},{\bf r}')$ we use the Ornstein-Zernike equation, and the two equations constitute a general liquid-state framework for treating inhomogeneous fluids. As the two equations do not form a closed set, an approximate closure relation is required and it determines a type of an approximation. In the present work we investigate the random phase approximation (RPA) closure. We determine th…
It is known that homogeneous distribution of particles in Coulomb-like systems can be unstable, and spatially inhomogeneous structures can be formed. A simple method for describing such inhomogeneous systems and obtaining spacial distributions of electron density is proposed and applied to the case of two-dimensional electron systems on surface of liquid helium. A free energy functional for the model in mean field approximation is obtained. Creation of various types of structures, such as long-range periodical modulation and multi-electron dimples, is predicted by minimizing this functional.
Building on the recently derived inhomogeneous mode-coupling theory, we extend the generalised mode-coupling theory of supercooled liquids to inhomogeneous environments. This provides a first-principles-based, systematic and rigorous way of deriving high-point dynamical susceptibilities from variations of the many-body dynamic structure factors with respect to their conjugate field. This new framework allows for a novel and fully microscopic possibility to probe for collective relaxation mechanisms in supercooled liquids near the mode-coupling glass transition.
It is shown that in adiabatic approximation for nuclei the many-component Coulomb system cannot be described on the basis of the grand canonical ensemble. Using the variational Bogolyubov's procedure for the free energy, the Hohenberg-Kohn theorem is proved in the canonical ensemble for inhomogeneous electron gas at finite temperature. The principal difference between consideration in the framework of quantum statistics in the canonical ensemble and quantum-mechanical consideration of a finite number of particles in infinite volume is established. The problem of universality of the density fun…
Spin-density-functional theory (SDFT) is the most widely implemented and applied formulation of density-functional theory. However, it is still finding novel applications, and occasionally encounters unexpected problems. In this paper we first briefly describe a few of the latter, related to issues such as nonuniqueness, noncollinearity, and currents. In the main part we then turn to an example of the former, namely SDFT for the Heisenberg model. It is shown that time-honored concepts of Coulomb DFT, such as the local-density approximation, can be applied to this (and other) model Hamiltonians…
When a fluid is subject to an external field, as is the case near an interface or under spatial confinement, then the density becomes spatially inhomogeneous. Although the one-body density provides much useful information, a higher level of resolution is provided by the two-body correlations. These give a statistical description of the internal microstructure of the fluid and enable calculation of the average interparticle force, which plays an essential role in determining both the equilibrium and dynamic properties of interacting fluids. We present a theoretical framework for the description…
The dynamics of a confined fluid of Bose atoms is treated within the linear response regime, with a view to establishing a current-density functional formalism for an inhomogeneous superfluid state. After evaluating in full detail a simplified case of an external coupling to the density and phase of the condensate, the theory is extended to include the coupling to the total current density. The Kohn-Sham response functions of the condensate and all the exchange-correlation kernels for the superfluid are introduced from the microscopic equations of motion and are expressed in a physically trans…
The authors present a study of the non equilibrium statistical properties of a one dimensional hard-rod fluid dissipating energy via inelastic collisions and subject to the action of a Gaussian heat bath, simulating an external driving mechanism. They show that the description of the fluid based on the one-particle phase-space reduced distribution function, in principle necessary because of the presence of velocity dependent collisional dissipation, can be contracted to a simpler description in configurational space. Indeed, by means of a multiple-time scale method the authors derive a self-co…
We study adsorption of liquid at a one-dimensional substrate composed of a single chemical inhomogeneity of width $2L$ placed on an otherwise homogeneous, planar, solid surface. The excess point free energy $η(L,T)$ associated with the adsorbed layer's inhomogeneity induced by the substrate's chemical structure is calculated within exact continuum transfer-matrix approach. It is shown that the way $η(L,T)$ varies with $L$ depends sensitively on the temperature regime. It exhibits logarithmic divergence as a function of $L$ in the limit $L\to\infty$ for temperatures such that the chemical inhom…
We extend a recently introduced free-energy formalism for homogeneous Fokker-Planck equations to a wide, and physically appealing, class of inhomogeneous nonlinear Fokker-Planck equations. In our approach, the free-energy functional is expressed in terms of an entropic functional and an auxiliary potential, both derived from the coefficients of the equation. With reference to the introduced entropic functional, we discuss the entropy production in a relaxation process towards equilibrium. The properties of the stationary solutions of the considered Fokker-Planck equations are also discussed.
A metastable state, characterized by a low degree of mass localization is identified using Density Functional Theory. This free energy minimum, located through the proper evaluation of the competing terms in the free energy functional, is independent of the specific form of the DFT used. Computer simulation results on particle motion indicate that this heterogeneous state corresponds to the supercooled state.
A finite-temperature density functional approach to describe the properties of parahydrogen in the liquid-vapor coexistence region is presented. The first proposed functional is zero-range, where the density-gradient term is adjusted so as to reproduce the surface tension of the liquid-vapor interface at low temperature. The second functional is finite-range and, while it is fitted to reproduce bulk pH2 properties only, it is shown to yield surface properties in good agreement with experiments. These functionals are used to study the surface thickness of the liquid-vapor interface, the wetting…
We present a derivation of the kinetic equation describing the secular evolution of spatially inhomogeneous systems with long-range interactions, the so-called inhomogeneous Landau equation, by relying on a functional integral formalism. We start from the BBGKY hierarchy derived from the Liouville equation. At the order ${1/N}$, where $N$ is the number of particles, the evolution of the system is characterised by its 1-body distribution function and its 2-body correlation function. Introducing associated auxiliary fields, the evolution of these quantities may be rewritten as a traditional func…
A unified formulation of the density functional theory is constructed on the foundations of entropic inference in both the classical and the quantum regimes. The theory is introduced as an application of entropic inference for inhomogeneous fluids in thermal equilibrium. It is shown that entropic inference reproduces the variational principle of DFT when information about expected density of particles is imposed. In the classical regime, this process introduces a family of trial density-parametrized probability distributions, and consequently a trial entropy, from which the preferred one is fo…
Starting from Newton's equations of motion, we derive a dynamical density functional theory (DDFT) applicable to atomic liquids. The theory has the feature that it requires as input the Helmholtz free energy functional from equilibrium density functional theory. This means that, given a reliable equilibrium free energy functional, the correct equilibrium fluid density profile is guaranteed. We show that when the isothermal compressibility is small, the DDFT generates the correct value for the speed of sound in a dense liquid. We also interpret the theory as a dynamical equation for a coarse gr…
This paper presents a unified method for formulating a field-theoretic perturbation theory that encompasses the conventional liquid state theory. First, the free-energy functional of instantaneous correlation field is obtained from the functional-integral representation of the grand potential. Next, we demonstrate that the instantaneous free-energy functional yields a closure relation between the correlation functions in the mean-field approximation. Notably, the obtained closure relation covers a variety of approximate closures introduced in the liquid state theory.
Based on the Schrodinger equation, exact expressions for the non-relativistic particle energy in the local external field and the external field potential are derived as inhomogeneous density functionals. On this basis, it is shown that, when considering more than two noninteracting electrons, the energy of such a system cannot be an inhomogeneous density functional. This means that the Hohenberg-Kohn lemma which assert that in the ground state to each inhomogeneous density corresponds only one potential of the external field cannot be a justification of the existence of the universal density …
Recently, based on the method of collective variables the statistical field theory for multicomponent inhomogeneous systems was formulated [O. Patsahan, I. Mryglod, J.-M. Caillol, Journal of Physical Studies, 2007, 11, 133]. In this letter we establish a link between this approach and the classical density functional theory for inhomogeneous fluids.
The response of Newtonian liquids to small perturbations is usually considered to be fully described by homogeneous transport coefficients like shear and dilatational viscosity. However, the presence of strong density gradients at the liquid/vapor boundary of fluids hints at the possible existence of an inhomogeneous viscosity. Here, we show that a surface viscosity emerges from the collective dynamics of interfacial layers in molecular simulations of simple liquids. We estimate the surface viscosity to be 8-16 times smaller than that of the bulk fluid at the thermodynamic point considered. Th…
Based on the Schrodinger equation, exact expressions for the non-relativistic particle energy in the local external field and the external field potential are derived as inhomogeneous density functionals. On this basis, it is shown that, when considering more than two noninteracting electrons, the energy of such a system cannot be an inhomogeneous density functional. The result is extended for the system of interacting electrons. This means that the Hohenberg-Kohn lemma which assert that in the ground state to each inhomogeneous density corresponds only one potential of the external field cann…
We calculate the ground-state energy of one and two-dimensional spatially inhomogeneous antiferromagnetic Heisenberg models for spins 1/2, 1, 3/2 and 2. Our calculations become possible as a consequence of the recent formulation of density-functional theory for Heisenberg models. The method is similar to spin-density-functional theory, but employs a local-density-type approximation designed specifically for the Heisenberg model, allowing us to explore parameter regimes that are hard to access by traditional methods, and to consider complications that are important specifically for nanomagnetic…
Replica Field Theory for a Generalized Franz--Parisi Potential of Inhomogeneous Glassy Systems: New Closure and the Associated Self-Consistent Equation
Heterogeneous nucleation is studied by Monte Carlo simulations and phenomenological theory, using the two-dimensional lattice gas model with suitable boundary fields. A chemical inhomogeneity of length b at one boundary favors the liquid phase, while elsewhere the vapor is favored. Switching on the bulk field favoring the liquid, nucleation and growth of the liquid phase starting from the region of the chemical inhomogeneity is analyzed. Three regimes occur: for small fields, the critical droplet radius is so large that a critical droplet having the contact angle required by Young's equation i…
We use a wave functional approach to calculate the fidelity of ground states in the Luttinger liquid universality class of one-dimensional gapless quantum many-body systems. The ground-state wave functionals are discussed using both the Schrodinger (functional differential equation) formulation and a path integral formulation. The fidelity between Luttinger liquids with Luttinger parameters K and K' is found to decay exponentially with system size, and to obey the symmetry F(K,K')=F(1/K,1/K') as a consequence of a duality in the bosonization description of Luttinger liquids.
In this article we show that the inhomogeneous density obtained from a density-functional theory of classical fluids in the canonical ensemble (CE), recently presented by White et al [Phys. Rev. Lett. 84 (2000) 1220], is equivalent to first order to the result of the series expansion of the CE inhomogeneous density introduced by Gonzalez et al [Phys. Rev. Lett. 79 (1997) 2466].
An analysis shows that the ground state of the inhomogeneous system of interacting electrons in the static external field, which satisfies the thermodynamic limit, can be consistently described only using the Green function theory based on the quantum field theory methods (perturbation theory diagram technique). In this case, the ground state energy and inhomogeneous electron density in such a system can be determined only after calculating the single-particle Green function.
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. T…
Density-functional theory is applied to compute the ground-state energies of quantum hard-sphere solids. The modified weighted-density approximation is used to map both the Bose and the Fermi solid onto a corresponding uniform Bose liquid, assuming negligible exchange for the Fermi solid. The required liquid-state input data are obtained from a paired phonon analysis and the Feynman approximation, connecting the static structure factor and the linear response function. The Fermi liquid is treated by the Wu-Feenberg cluster expansion, which approximately accounts for the effects of antisymmetry…
A statistical field theory for an inhomogeneous liquid, a planar liquid/vapor interface, is devised from first principles. The grand canonical partition function is represented via a Hubbard-Stratonovitch tranformation leading, close to the critical point, to the usual $ϕ^4$ scalar field theory which is then rigorously considered at the one-loop level. When further simplified it yields the well-known capillary wave theory without any ad hoc phenomenological parameter. Internal coherence of the one-loop approximation is discussed and good overall qualitative agreement with recent numerical simu…
By the density functional theory for crystallization, it is shown that for vortex lines in an underlying layered structure a smectic phase with period m=2 can be stabilized by strong layer pinning. The freezing of vortex liquid is then two-step, a second-order liquid-smectic transition and a first-order smectic-lattice transition. DFT also indicates that a direct, first-order liquid-lattice transition preempts the smectic order with m>2 irrespectively of the pinning strength. Possible H-T phase diagrams are mapped out. Implications of the DFT results to the interlayer Josephson vortex system i…
Motivated by the calculation of correlation functions in inhomogeneous one-dimensional (1d) quantum systems, the 2d Inhomogeneous Gaussian Free Field (IGFF) is studied and solved. The IGFF is defined in a domain $Ω\subset \mathbb{R}^2$ equipped with a conformal class of metrics $[{\rm g}]$ and with a real positive coupling constant $K: Ω\rightarrow \mathbb{R}_{>0}$ by the action $\mathcal{S}[h] = \frac{1}{8π} \int_Ω\frac{\sqrt{\rm g} d^2 {\rm x}}{K({\rm x})} \, {\rm g}^{i j} (\partial_i h)(\partial_j h)$. All correlations functions of the IGFF are expressible in terms of the Green's functions …
