On the relationship between the density functional formalism and the potential distribution theory for nonuniform fluids

It is shown that the variational principle for the grand potential of a nonuniform fluid as a functional of the singlet density yields the potential distribution theory for the equilibrium density. We derive the explicit form that the functional takes for a system of hard rods, and propose an approximate one for hard spheres. Attractive interactions are also considered in mean-field approximation. In all cases the pair direct correlation function of the nonuniform system is obtained and the density gradient expansion of the free energy is investigated.     

Approximate solutions of the Liouville equation. II. Stationary variational principles

Stationary variational functionals for the Laplace transform of the Liouville distribution are constructed. The value of the functional is the autocorrelation function that one wishes to compute. It is shown that the functionals may be transformed to a renormalized form. Trial functions not involving the potential explicitly give rise to time-dependent autocorrelation functions determined only by equilibrium spatial correlation functions. Another class of functionals is constructed by independently varying the parity symmetric and antisymmetric parts of the distribution function. Trial functions need only be assumed for one of these—the optimum value of the other one is given exactly. This procedure is used to improve the simplest known theories for velocity and density autocorrelation functions.Work supported by a grant from the National Science Foundation.     

Equilibrium theory of molecular fluids: Structure and freezing transitions

In this article we review equilibrium theory of molecular fluids which includes structure and freezing transitions. The application of the theory to evaluate the pair correlation functions using Integral Equation methods and Computer Simulations have been discussed. Freezing of classical complex fluids based on the density functional approach is also discussed and compare a variety of its versions. Transitions discussed are sensitive to the value of direct correlation functions of the effective liquid which is required as an input information in the theory. Accurate evaluation of pair correlation functions is emphasized. Calculation of these correlation functions which pose problems in the case of ordered phases is discussed. The pair correlation functions of the ordered phase, which are supposed to be made up of two contributions, one that preserves the symmetry of the isotropic phase and a second that breaks it, are discussed. A new free-energy functional developed for an inhomogeneous system that contains both symmetry conserved and symmetry broken parts of the direct pair correlation function is discussed. The most useful three dimensional reference interaction site model (3D-RISM) and its extension done recently by many workers is discussed. Application of this theory to a large variety of complex systems in combination with the density functional theory method implemented in the Amsterdam density functional software package is discussed. Coupling of the 3D-RISM salvation theory with molecular dynamics in the Amber molecular dynamics package is also given.     

Variational Principle in the Theory of Partial Distribution Functions

We have constructed thermodynamically consistent theory of correlations in a classical equilibrium system. The theory is based on a variational principle for thermodynamic potential, as functional of correlation functions. Both the thermodynamic potential and correlation functions are determined simultaneously from a uniform variation problem for this functional. We have offered also methods of consecutive approximations system construction for the solution of the obtained variational problem.     

Classical density functional theory meets Monte-Carlo simulations

ABSTRACT

Typically the quality of an approximate density functional is evaluated by a direct comparison of its predictions in a given test case to exact data obtained by computer simulations. An important example for such an approach is the test of equilibrium structure of a simple fluid as measured by the pair distribution function g(r) or the cavity correlation function y(r). However, the combination of exact density profiles and the analytical structure of density functional theory allows one to determine and potentially improve the quality of a functional in a more sophisticatedway.     

Diagrammatic analysis of correlations in polymer fluids: Cluster diagrams via Edwards’ field theory

Edwards’ functional integral approach to the statistical mechanics of polymer liquids is amenable to a diagrammatic analysis in which free energies and correlation functions are expanded as infinite sums of Feynman diagrams. This analysis is shown to lead naturally to a perturbative cluster expansion that is closely related to the Mayer cluster expansion developed for molecular liquids by Chandler and co-workers. Expansion of the functional integral representation of the grand-canonical partition function yields a perturbation theory in which all quantities of interest are expressed as functionals of a monomer-monomer pair potential, as functionals of intramolecular correlation functions of non-interacting molecules, and as functions of molecular activities. In different variants of the theory, the pair potential may be either a bare or a screened potential. A series of topological reductions yields a renormalized diagrammatic expansion in which collective correlation functions are instead expressed diagrammatically as functionals of the true single-molecule correlation functions in the interacting fluid, and as functions of molecular number density. Similar renormalized expansions are also obtained for a collective Ornstein-Zernicke direct correlation function, and for intramolecular correlation functions. A concise discussion is given of the corresponding Mayer cluster expansion, and of the relationship between the Mayer and perturbative cluster expansions for liquids of flexible molecules. The application of the perturbative cluster expansion to coarse-grained models of dense multi-component polymer liquids is discussed, and a justification is given for the use of a loop expansion. As an example, the formalism is used to derive a new expression for the wave-number dependent direct correlation function and recover known expressions for the intramolecular two-point correlation function to first-order in a renormalized loop expansion for coarse-grained models of binary homopolymer blends and diblock copolymer melts.     

A simple and realistic triton wave function

We propose a simple triton wave function that consists of a product of three correlation operators operating on a three-body spin-isospin state. This wave function is formally similar to that used in the recent variational theories of nuclear matter, the main difference being in the long-range behavior of the correlation operators. Variational calculations are carried out with the Reid potential, using this wave function in the so-called “symmetrized product” and “independent pair” forms. The triton energy and density distributions obtained with the symmetrized product wave function agree with those obtained in Faddeev and other variational calculations using harmonic oscillator states. The proposed wave function and calculational methods can be easily generalized to treat the four-nucleon α-particle.     

自由界面等离子体平衡的变分原理

在自由界面情况下用求位能汛函极值的变分原理推出了等离子体平衡所需满足的平衡方程和边界条件;其泛函的Euler方程即为具有自由界面条件的磁面函数方程。也给出了便于计算的变分泛函,它相当于等值面边界问题。对于导体壁为简单几何形状的情况,用Rit法进行了数值计算。 关键词：     

Pair correlations of an expanding superfluid Fermi gas

The pair correlation function of an expanding gas is investigated with an emphasis on the BEC-BCS crossover of a superfluid Fermi gas at zero temperature. At unitarity quantum Monte Carlo simulations reveal the occurrence of a sizable bunching effect due to interactions in the spin up-down channel which, at short distances, is larger than that exhibited by thermal bosons in the Hanbury-Brown-Twiss effect. We propose a local equilibrium ansatz for the pair correlation function which we predict will remain isotropic during the expansion even if the trapping potential is anisotropic, in contrast with the behavior of the density. The isotropy of the pair correlation function is an experimentally accessible signature, which makes a clear distinction with respect to the case of noninteracting gases and can be understood as a consequence of the violation of scaling.     

Critical analysis of the Colle-Salvetti model for electron correlation in closed shell systems: pair correlations

The Colle-Salvetti functional for electron correlation in closed shell systems is applied to a simple two-electron problem and compared with a variational wavefunction. The correlation hole is found to be too short range. As a result, the model is biased towards regions of large electron density and practically neglects pair correlations that are long range. In addition, the correlation energy per electron is found to be singular at the nucleus. The error from neglecting the single-particle operators is found to be of the order of magnitude of the correlation energy itself. It is concluded that the Colle-Salvetti model predicts inaccurate pair correlations and should be used with great care.     

Variational path integral approach to the ground state energy of artificial atoms

Artificial atoms in different confinement potentials are studied using the Jensen–Feynman variational approach. The density and pair correlation function of an harmonic model with statistics are analytically calculated and used to find the variational ground state energy in two and three dimensions. The results are compared with the numerical calculations and a good correlation is found.     

金属表面的相关波函数理论(Ⅰ)——理论框架

本文给出具有长程库伦作用的非均匀体系(金属表面)的相关波函数的理论框架。表面的波函数是两部份的乘积,一部份是在满足系统空间对称性的变分势下的单电子波函数组成的行列式;另一部份是Feenberg-Jastrow关联因子。本文给出在“jellium”模型下的金属表面能量公式以及在不考虑Feenberg-Jastrow关联因子下(“无相互作用”情形)的电子密度分布公式。 关键词：     

Variational pair theory of the attractive and extended Hubbard model ind-dimensions

We present a variational approach for treating the Hubbard Hamiltonian in one, two and three dimensions. It is based on 2M-fermion wavefunctions which are allowed to form correlated spin-singlet pairs. Expressions for the ground state energy and correlation functions are derived in terms of general pair coefficient functions. The presented approach offers a convenient starting point for improved variational treatments that allow to include different specific types of pair correlations. We present first applications to the attractive and to the extended Hubbard model using a very simple ansatz for the pair coefficient functions. The ground state energy, chemical potential, order parameter, momentum distribution as well as spin-spin and density-density correlation functions follow from a system of coupled nonlinear equations that has to be solved selfconsistently. All quantities are given for arbitrary band-filling in one, two and three dimensions. Our results are compared with those of other approximations and for the one-dimensional case with the exact results of Krivnov and Ovchinnikov.     

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 (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The nonuniform hard-rod fluid revisited

The statistical mechanics of the one-dimensional nonuniform pure hard-core fluid is formulated in the spirit of the Reiss-Frisch-Lebowitz (RFL) scaled particle theory. By emphasizing the importance of the core dependence, a more intuitive and simpler derivation can be given. The Wiener-Hopf-type construction of the pair direct correlation function is formulated via the Dyson variational method of inverse scattering theory, which is compared with the particle-hole theory. The new approach allows us to lift the global free energy functional into a larger space where all the symmetries become apparent.     

Direct correlation function in equilibrium polymers by PRISM equations

In this work, we calculate the direct correlation function and the structure factor of equilibrium polymers in the framework of the PRISM theory. We study especially the effect of the polydispersity and the monomer density on these functions. The intermolecular pair distribution function is compared with simulation results using a recent equilibrium polymer chains model. A scaling analysis is carried out for the direct correlation function.     

Fluctuations and stability of stationary non-equilibrium systems in detailed balance

A generalized thermodynamic potential for Markoffian systems with detailed balance and far from thermal equilibrium has been derived in a previous paper. It was shown that the principle of detailed balance is equivalent to a set of conditions fulfilled by this potential (“potential conditions”). The properties of this potential allow us to extend the validity of a number of thermodynamic concepts well known for systems in or near thermal equilibrium to stationary states far from thermal equilibrium. The concept of symmetry breaking phase transitions for these systems is introduced in analogy to thermal equilibrium systems by considering the dependence of the stationary probability density of the system on a set of externally controlled parameters {λ}. A functional of the time dependent probability density of the system is defined in close analogy to the Gibb's definition of entropy. This functional has the properties of a Ljapunov functional of the governing Fokker-Planck equation showing the stability of the stationary probability density. The Langevin equations connected with the Fokker-Planck equation are considered. It is shown that, by means of the potential conditions, generalized “thermodynamic” fluxes and forces may be defined in such a way that the smoothly varying part of the Langevin equations (kinetic equations) constitutes a linear relation between fluxes and forces. The matrix of coefficients is given by the diffusion matrix of the Fokker-Planck equation. The symmetry relations which hold for this matrix due to the potential conditions then lead to the Onsager-Casimir symmetry relations extended to systems with detailed balance near stationary states far from thermal equilibrium. Finally it is shown that under certain additional assumptions the generalized thermodynamic potential may be used as a Ljapunov function of the kinetic equations.     

Irreversible thermodynamics of fluids

Irreversible thermodynamics of fluids is formulated based on a set of postulates. The theory thus constructed generalizes thermostatics and linear irreversible thermodynamics into the realm of nonlinear irreversible processes. In this theory the extended Gibbs relation and the entropy balance equation appear as a pair of mutually consistent equations under the postulates made. An equivalent theory is also formulated by replacing one of the postulates with another that is basically a variational principle. The variational principle yields the evolution equations for fluxes as the Euler equations that extremize the variational functional postulated. The local form of the extremized variational functional is the entropy balance equation for the irreversible processes in the system. Some further consequences of the theory are also considered. For example, nonequilibrium specific heats are shown to be at least quadratic functions of fluxes and reduce to the equilibrium specific heats in the limit of vanishing fluxes. In order to illustrate an example of possible applications, we have considered nonlinear transport processes in fluids. The connections of the present theory with other theories are discussed.     

Electric-dipole sum rule in nuclear matter

The enhancement factor K in the electric-dipole sum rule for some realistic models of symmetrical nuclear matter is calculated using variational theory. The nuclear-matter wave function used contains central, spin, isospin, tensor and spin-orbit pair correlations. The non-central correlations, particularly the tensor one, give the major contribution to K. At experimental equilibrium density K. turns out to be ≈ 1.8, of which 65% comes from OPEP and 30% from the short-range part of the interaction. The two-pion-exchange three-nucleon interaction contributes ≈ 0.2% and is cancelled, to a large extent, by the contribution due to the intermediate-range two-body potential. The relationship of the summed oscillator strength with the effective mass is also discussed.     

Spatial correlation of two particles in semiconductor quantum ring

We analyze the effect of the spatial correlation on the ground state energy of two particles (two electrons and exciton–hole pair) confined in quantum ring (QR) with a soft-edge-barrier confinement potential. Starting from the Schrödinger variational principle we derive a one-dimensional differential equation for the spatial pair correlation function (SPCF), which we solve numerically by using the shooting method. The effect of the repulsive core in a self-assembled GaAs/InAs QR on the two-electron and exciton SPCF is analyzed. A comparative analysis of the dependencies of the two-particle ground state energies on the inner and outer radii of GaAs/InAs QRs with different confinement potential shapes is presented.