Freezing in the presence of a periodic external potential

The density functional theory of freezing of hard spheres is extended to the case where the system is submitted to a given external potential of low lattice symmetry. It is shown that this constraint is very effective in stabilizing the low density metastable hard sphere solid.     

On the Problem of Universal Density Functional

A performed analysis shows that the density functional theory for the inhomogeneous electron gas, which is based on the hypothesis of the existence of the density functional for the external field potential is incorrect. This means that the density functional theory is not an ab initio theory.     

The influence of random changes in the adsorbing potential on phase transitions in a Lennard-Jones fluid confined to energetically heterogeneous slit-like pores

A density functional approach is used to study the adsorption and phase behaviour of a Lennard-Jones (LJ) fluid in slit-like pores with energetically heterogeneous walls, investigating how the randomly varying part of the fluid-solid potential imposed on a periodic ‘back-ground’ potential modifies the phase behaviour of the confined fluid. Non-local density functional theory is employed to describe the system. To study the system with a random external field, the method used is based on investigations of several replicas of the system and on averaging the final thermodynamic results over the replicas.     

Statistical Mechanics Approach for Uniform and Non-uniform Fluid with Hard Core and Interaction Tail

One recently proposed self-consistent hard sphere bridge functional was combined with an exponential function exp(-cr) and a re-normalized indirect correlation function to construct the bridge function for fluid with hard core and interaction tail. In the present approach, the adjustable parameter α was determined by the thermodynamic consistency realized on the compressibility modulus, the re-normalization of the indirect correlation function was realized by a modified Mayer function with the interaction potential replaced by the perturbative part of the interaction potential. As an example, the present bridge function was combined with the Ornstein-Zernike (OZ) equation to predict structure and thermodynamics properties in very good agreement with the simulation data available for Lennard-Jones (L J). Based on the universality principle of the free energy density functional and the test particle trick, the numerical solution of the OZ equation was employed to construct the first order direct correlation function of the non-uniform fluid as a functional of the density distribution by means of the indirect correlation function. In the framework of the density functional theory, the numerically obtained functional predicted the density distribution of LJ fluid confined in two planar hard walls that is in good agreement with the simulation data.     

核物质四阶对称能中的交换项相关物理

基于协变密度泛函（CDF）理论,核物质四阶对称能可以被分解为动能部分,同位旋单态势能部分以及同位旋三重态势能部分。交换项的引入明显改变了同位旋单态势能部分和同位旋三重态势能部分的密度行为,特别是来自同位旋标量介子-核子耦合道的交换项贡献提供了一个压制作用。作为一种有益的尝试,引入广义的对称能,可以更直观地统一描述核物质各阶对称能效应。The density dependence of nuclear fourth-order symmetry energy S₄ is studied within the covariant density functional (CDF) theory in terms of the kinetic energy, isospin-singlet, and isospin-triplet potential energy parts of the energy density functional. When the Fock diagram is introduced, it is found that both isospin-singlet and isospin-triplet components of the potential energy plays important roles in determining the fourth-order symmetry energy. Especially, an extra suppression, which comes from the Fock terms via isoscalar meson-nucleon coupling channels, is revealed in the isospin-triplet potential part of the fourth-order symmetry energy. As an useful attempt, the generalized symmetry energy is introduced to describe the various orders of nuclear symmetry energies in a visual and self-consistent way.     

Derivation of a proximity interaction between nuclei from the Hartree-Fock functional with Skyrme interactions

The potential between heavy or medium heavy spherical nuclei is derived on the basis of the proximity approximation and the assumption of undisturbed spherical density distributions. The HF-theory with Skyrme forces is used to write the energy as a functional of the density. The resulting potential consists of an isoscalar and a (much smaller) isospin-dependent part. Depending on the choice of the Skyrme parameters calculated interaction between heavy ions are close to the double folding potential or to the proximity potential. Our interaction can be factorized with a very good approximation into scaling factors and universal functions of the proximity distance in units of the surface thickness.     

Exact density-functional potentials for time-dependent quasiparticles

We calculate the exact Kohn-Sham potential that describes, within time-dependent density-functional theory, the propagation of an electron quasiparticle wave packet of nonzero crystal momentum added to a ground-state model semiconductor. The potential is observed to have a highly nonlocal functional dependence on the charge density, in both space and time, giving rise to features entirely lacking in local or adiabatic approximations. The dependence of the nonequilibrium part of the Kohn-Sham electric field on the local current and charge density is identified as a key element of the correct Kohn-Sham functional.     

Prediction of the derivative discontinuity in density functional theory from an electrostatic description of the exchange and correlation potential

We propose an approach to approximate the exchange and correlation (XC) term in density functional theory. The XC potential is considered as an electrostatic potential, generated by a fictitious XC density, which is in turn a functional of the electronic density. We apply the approach to develop a correction scheme that fixes the asymptotic behavior of any approximated XC potential for finite systems. Additionally, the correction procedure gives the value of the XC derivative discontinuity; therefore, it can directly predict the fundamental gap as a ground-state property.     

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.     

团簇LaO的理论研究

采用密度泛函理论研究LaO团簇体系。中性分子LaO的基态是两重态(2Σ),阴离子LaO-和阳离子LaO 的基态都是单重态(1Σ)。使用不同的方法计算团簇LaO的电子亲和能和电离能。计算结果表明用BLYP方法和弥散极化基组计算结果和实验数据吻合较好。用含时密度泛函理论计算团簇LaO的低能激发态,从理论上归属LaO-的光电子能谱的谱峰和LaO的吸收光谱的谱峰。计算得到与实验一致的结果。     

Potential functionals: dual to density functionals and solution to the v-representability problem

A functional of external potentials and its variational principle for the ground-state energy is constructed. This potential functional formulation is dual to the density functional approach and provides a solution to the v-representability problem in the original Hohenberg-Kohn theory. A second potential functional for Kohn-Sham noninteracting systems establishes the foundation for the optimized effective potential approach and results in efficient approaches for ensemble Kohn-Sham calculations.     

Self-consistent scattering theoretical method for surfaces: Application to Si(100)

We have developed a method for solving self-consistently the Green's-function equations describing a semiinfinite crystal within local density functional formalism. Based on scattering theory, it yields the potential, charge density, wavevector-resolved layer state densities and the energy spectrum of the surface. A detailed study of the ideal Si(100) surface illustrates the approach and sheds light on differences in previous self-consistent results of matching and supercell calculations for this very surface.     

Reformulation of density functional theory for N-representable densities and the resolution of the v-representability problem

Density functional theory for the case of general, N-representable densities is reformulated in terms of density functional derivatives of expectation values of operators evaluated with wave functions leading to a density, making no reference to the concept of potential. The developments provide proof of existence of a mathematical procedure that determines whether a density is v-representable and in the case of an affirmative answer determines the potential (within an additive constant) as a derivative with respect to the density of a constrained search functional. It also establishes the existence of an energy functional of the density that, for v-representable densities, assumes its minimum value at the density describing the ground state of an interacting many-particle system. The theorems of Hohenberg and Kohn emerge as special cases of the formalism. Numerical results for one-dimensional non-interacting systems illustrate the formalism. Some direct formal and practical implications of the present reformulation of DFT are also discussed.     

Direct measurement of entropic forces induced by rigid rods

We present the first direct depletion potential measurements for a single colloidal sphere close to a wall in a suspension of rigid colloidal rods. Since all particle interactions are as good as hard-core-like, the depletion potentials are of entirely entropic origin. We developed a density functional theory approach that accurately accounts for this experimental situation. The depletion potentials calculated for different rod number densities are in very good quantitative agreement with the experimental results.     

Solving the ultranonlocality problem in time-dependent spin-density-functional theory

It has been known for some time that the exchange-correlation potential in time-dependent density-functional theory is an intrinsically nonlocal functional of the density as soon as one goes beyond the adiabatic approximation. In this paper we show that a much more severe nonlocality problem, with a completely different physical origin, plagues the exchange-correlation potentials in time-dependent spin-density functional theory. We show how the use of the spin current density as a basic variable solves this problem, and we provide an explicit local expression for the exchange-correlation fields as functionals of the spin currents.     

m-BiVO_4与t-BiVO_4的电子结构和光学性质的第一性原理研究

采用第一性原理的密度泛函理论赝势平面波方法,计算了单斜m-BiVO_4与四方t-BiVO_4的电子结构和光学性质.计算结果表明:m-BiVO_4为间接带隙半导体,禁带宽度为2.171 e V,t-BiVO_4为直接带隙半导体,禁带宽度为2.644 e V;m-BiVO_4与t-BiVO_4均可吸收紫外光及可见光,m-BiVO_4还可以吸收部分红外光.