Optimized local basis set for Kohn–Sham density functional theory

We develop a technique for generating a set of optimized local basis functions to solve models in the Kohn–Sham density functional theory for both insulating and metallic systems. The optimized local basis functions are obtained by solving a minimization problem in an admissible set determined by a large number of primitive basis functions. Using the optimized local basis set, the electron energy and the atomic force can be calculated accurately with a small number of basis functions. The Pulay force is systematically controlled and is not required to be calculated, which makes the optimized local basis set an ideal tool for ab initio molecular dynamics and structure optimization. We also propose a preconditioned Newton–GMRES method to obtain the optimized local basis functions in practice. The optimized local basis set is able to achieve high accuracy with a small number of basis functions per atom when applied to a one dimensional model problem.     

A mesh-free convex approximation scheme for Kohn–Sham density functional theory

Density functional theory developed by Hohenberg, Kohn and Sham is a widely accepted, reliable ab initio method. We present a non-periodic, real space, mesh-free convex approximation scheme for Kohn–Sham density functional theory. We rewrite the original variational problem as a saddle point problem and discretize it using basis functions which form the Pareto optimum between competing objectives of maximizing entropy and minimizing the total width of the approximation scheme. We show the utility of the approximation scheme in performing both all-electron and pseudopotential calculations, the results of which are in good agreement with literature.     

On a solution of the self-interaction problem in Kohn–Sham density functional theory

We report on a methodology for the treatment of the Coulomb energy and potential in Kohn–Sham density functional theory that is free from self-interaction effects. Specifically, we determine the Coulomb potential given as the functional derivative of the Coulomb energy with respect to the density, where the Coulomb energy is calculated explicitly in terms of the pair density of the Kohn–Sham orbitals. This is accomplished by taking advantage of an orthonormal and complete basis that is an explicit functional of the density that then allows for the functional differentiation of the pair density with respect to the density to be performed explicitly. This approach leads to a new formalism that provides an analytic, closed-form determination of the exchange potential. This method is applied to one-dimensional model systems and to the atoms Helium through Krypton based on an exchange only implementation. Comparison of our total energies (denoted SIF) to those obtained using the usual Hartree–Fock (HF) and optimized effective potential (OEP) methods reveals the hierarchy $E_{\mathrm{HF}}\le E_{\mathrm{OEP}}\le E_{\mathrm{SIF}}$ that is indicative of the greater variation freedom implicit in the former two methods.     

Solving the self-interaction problem in Kohn–Sham density functional theory: Application to atoms

In previous work, we proposed a computational methodology that addresses the elimination of the self-interaction error from the Kohn–Sham formulation of the density functional theory. We demonstrated how the exchange potential can be obtained, and presented results of calculations for atomic systems up to Kr carried out within a Cartesian coordinate system. In this paper, we provide complete details of this self-interaction free method formulated in spherical coordinates based on the explicit equidensity basis ansatz. We prove analytically that derivatives obtained using this method satisfy the Virial theorem for spherical orbitals, where the problem can be reduced to one dimension. We present the results of calculations of ground-state energies of atomic systems throughout the periodic table carried out within the exchange-only mode.     

Kohn–Sham density functional inspired approach to nuclear binding

A non-relativistic nuclear density functional theory is constructed, not as done most of the time, from an effective density dependent nucleon–nucleon force but directly introducing in the functional results from microscopic nuclear and neutron matter Bruckner G-matrix calculations at various densities. A purely phenomenological finite range part to account for surface properties is added. The striking result is that only four to five adjustable parameters, spin–orbit included, suffice to reproduce nuclear binding energies and radii with the same quality as obtained with the most performant effective forces. In this pilot work, for the pairing correlations, simply a density dependent zero range force is adopted from the literature. Possible future extensions of this approach are pointed out.     

A Kohn–Sham equation solver based on hexahedral finite elements

We design a Kohn–Sham equation solver based on hexahedral finite element discretizations. The solver integrates three schemes proposed in this paper. The first scheme arranges one a priori locally-refined hexahedral mesh with appropriate multiresolution. The second one is a modified mass-lumping procedure which accelerates the diagonalization in the self-consistent field iteration. The third one is a finite element recovery method which enhances the eigenpair approximations with small extra work. We carry out numerical tests on each scheme to investigate the validity and efficiency, and then apply them to calculate the ground state total energies of nanosystems C₆₀, C₁₂₀, and C₂₇₅H₁₇₂. It is shown that our solver appears to be computationally attractive for finite element applications in electronic structure study.     

Eigenvalues,integer discontinuities and NMR shielding constants in Kohn—Sham theory

Kohn—Sham eigenvalues are determined from coupled cluster electron densities. The calculated HOMO—LUMO eigenvalue differences are compared with those from conventional generalized gradient approximation (GGA) exchange-correlation functionals for a range of small molecules. In all cases, GGA HOMO—LUMO differences are smaller than those calculated from the coupled cluster densities. When the GGA HOMO—LUMO differences are explicitly corrected—such that they equal those calculated from electron densities—significant improvements in NMR shielding constants are obtained. The eigenvalues calculated from electron densities are also used to approximate the magnitude of the integer discontinuity in the exact exchange-correlation potential. The value of the Kohn—Sham HOMO eigenvalue is then considered. Although HOMO eigenvalues from high quality, asymptotically vanishing, exchange-correlation potentials are close to the negative of the ionization potential, HOMO eigenvalues from the GGA functionals are shifted upwards by approximately 50% of the calculated integer discontinuity. An alternative approach for correcting NMR shielding constants is investigated.     

Computationally simple,analytic, closed form solution of the Coulomb self-interaction problem in Kohn–Sham density functional theory

We have developed and tested in terms of atomic calculations an exact, analytic and computationally simple procedure for determining the functional derivative of the exchange energy with respect to the density in the implementation of the Kohn–Sham formulation of density functional theory (KS-DFT), providing an analytic, closed-form solution of the self-interaction problem in KS-DFT. We demonstrate the efficacy of our method through ground-state calculations of the exchange potential and energy for atomic He and Be atoms, and comparisons with experiment and the results obtained within the optimized effective potential (OEP) method.     

Atomic C 6 dispersion coefficients: a four-component relativistic Kohn–Sham study

We present C ₆ homo- and heteroatomic dispersion coefficients for all closed-shell atoms of the periodic table based on dipole–dipole polarizabilities at imaginary frequencies calculated using our recent extension of the complex polarization propagator approach to the four-component relativistic Kohn–Sham approach. Lack of proper reference data bars definite conclusions as to which density functional shows the overall best performance, and we therefore call for state-of-the-art wave function-based correlated calculations of dispersion coefficients. Scalar relativistic effects are significant already for elements as light as zinc, whereas spin–orbit effects must be taken into account only for very heavy elements.     

Adaptive local basis set for Kohn–Sham density functional theory in a discontinuous Galerkin framework I: Total energy calculation

Kohn–Sham density functional theory is one of the most widely used electronic structure theories. In the pseudopotential framework, uniform discretization of the Kohn–Sham Hamiltonian generally results in a large number of basis functions per atom in order to resolve the rapid oscillations of the Kohn–Sham orbitals around the nuclei. Previous attempts to reduce the number of basis functions per atom include the usage of atomic orbitals and similar objects, but the atomic orbitals generally require fine tuning in order to reach high accuracy. We present a novel discretization scheme that adaptively and systematically builds the rapid oscillations of the Kohn–Sham orbitals around the nuclei as well as environmental effects into the basis functions. The resulting basis functions are localized in the real space, and are discontinuous in the global domain. The continuous Kohn–Sham orbitals and the electron density are evaluated from the discontinuous basis functions using the discontinuous Galerkin (DG) framework. Our method is implemented in parallel and the current implementation is able to handle systems with at least thousands of atoms. Numerical examples indicate that our method can reach very high accuracy (less than 1 meV) with a very small number (4–40) of basis functions per atom.     

Light-matter interactions within the Ehrenfest–Maxwell–Pauli–Kohn–Sham framework: fundamentals,implementation, and nano-optical applications

In recent years significant experimental advances in nano-scale fabrication techniques and in available light sources have opened the possibility to study a vast set of novel light-matter interaction scenarios, including strong coupling cases. In many situations nowadays, classical electromagnetic modeling is insufficient as quantum effects, both in matter and light, start to play an important role. Instead, a fully self-consistent and microscopic coupling of light and matter becomes necessary. We provide here a critical review of current approaches for electromagnetic modeling, highlighting their limitations. We show how to overcome these limitations by introducing the theoretical foundations and the implementation details of a density-functional approach for coupled photons, electrons, and effective nuclei in non-relativistic quantum electrodynamics. Starting point of the formalism is a generalization of the Pauli–Fierz field theory for which we establish a one-to-one correspondence between external fields and internal variables. Based on this correspondence, we introduce a Kohn-Sham construction which provides a computationally feasible approach for ab-initio light-matter interactions. In the mean-field limit, the formalism reduces to coupled Ehrenfest–Maxwell–Pauli–Kohn–Sham equations. We present an implementation of the approach in the real-space real-time code Octopus using the Riemann–Silberstein formulation of classical electrodynamics to rewrite Maxwell's equations in Schrödinger form. This allows us to use existing very efficient time-evolution algorithms developed for quantum-mechanical systems also for Maxwell's equations. We show how to couple the time-evolution of the electromagnetic fields self-consistently with the quantum time-evolution of the electrons and nuclei. This approach is ideally suited for applications in nano-optics, nano-plasmonics, (photo) electrocatalysis, light-matter coupling in 2D materials, cases where laser pulses carry orbital angular momentum, or light-tailored chemical reactions in optical cavities just to name but a few.     

Bianchi type I cosmology in generalized Saez–Ballester theory via Noether gauge symmetry

In this paper, we investigate the generalized Saez–Ballester scalar–tensor theory of gravity via Noether gauge symmetry (NGS) in the background of Bianchi type I cosmological spacetime. We start with the Lagrangian of our model and calculate its gauge symmetries and corresponding invariant quantities. We obtain the potential function for the scalar field in the exponential form. For all the symmetries obtained, we determine the gauge functions corresponding to each gauge symmetry which include constant and dynamic gauge. We discuss cosmological implications of our model and show that it is compatible with the observational data.     

Time-dependent Ginzburg–Landau equations for multi-gap superconductors

We numerically solve the time-dependent Ginzburg–Landau equations for two-gap superconductors using the finite-element technique. The real-time simulation shows that at low magnetic field, the vortices in small-size samples tend to form clusters or other disorder structures. When the sample size is large, stripes appear in the pattern. These results are in good agreement with the previous experimental observations of the intriguing anomalous vortex pattern, providing a reliable theoretical basis for the future applications of multi-gap superconductors.     

Time-dependent Aharonov–Casher effect on noncommutative space

In this paper,we study the time-dependent Aharonov-Casher effect and its corrections due to spatial noncommutativity.Given that the charge of the infinite line in the Aharonov-Casher effect can adiabatically vary with time,we show that the original Aharonov-Casher phase receives an adiabatic correction,which is characterized by the time-dependent charge density.Based on Seiberg-Witten map,we show that noncommutative corrections to the time-dependent Aharonov-Casher phase contains not only an adi...     

Solution of Self-Consistent Kohn–Sham and Poisson Equations for Quasi Two-Dimensional Electron Gas in the Accumulation Layer of Semiconductor with Nonparabolic Conduction Band

Journal of Experimental and Theoretical Physics - We generalize the method proposed previously for a self-consistent solution of the system of the Kohn–Sham and Poisson equations to the case...     

Time-dependent Ginzburg–Landau equation in the Nambu–Jona-Lasinio model

We apply the closed time-path Green function formalism in the Nambu–Jona-Lasinio model. First of all, we use this formalism to obtain the well-known gap equation for the quark condensate in a stationary homogeneous system. We have also used this formalism to obtain the Ginzburg–Landau (GL) equation and the time-dependent Ginzburg–Landau (TDGL) equation for the chiral order parameter in an inhomogeneous system. In our derived GL and TDGL equations, there is no other parameters except for those in the original NJL model.     

Hohenberg–Kohn Theorems for Interactions,Spin and Temperature

Journal of Statistical Physics - We prove Hohenberg–Kohn theorems for several models of quantum mechanics. First, we show that for possibly degenerate systems of several types of particles,...