A spectral scheme for Kohn-Sham density functional theory of clusters

Starting from the observation that one of the most successful methods for solving the Kohn-Sham equations for periodic systems -- the plane-wave method -- is a spectral method based on eigenfunction expansion, we formulate a spectral method designed towards solving the Kohn-Sham equations for clusters. This allows for efficient calculation of the electronic structure of clusters (and molecules) with high accuracy and systematic convergence properties without the need for any artificial periodicity. The basis functions in this method form a complete orthonormal set and are expressible in terms of spherical harmonics and spherical Bessel functions. Computation of the occupied eigenstates of the discretized Kohn-Sham Hamiltonian is carried out using a combination of preconditioned block eigensolvers and Chebyshev polynomial filter accelerated subspace iterations. Several algorithmic and computational aspects of the method, including computation of the electrostatics terms and parallelization are discussed. We have implemented these methods and algorithms into an efficient and reliable package called ClusterES (Cluster Electronic Structure). A variety of benchmark calculations employing local and non-local pseudopotentials are carried out using our package and the results are compared to the literature. Convergence properties of the basis set are discussed through numerical examples. Computations involving large systems that contain thousands of electrons are demonstrated to highlight the efficacy of our methodology. The use of our method to study clusters with arbitrary point group symmetries is briefly discussed.Comment: Manuscript submitted (with revisions) to Journal of Computational Physic

Towards a Linear-Scaling DFT Technique: The Density Matrix Approach

A recently proposed linear-scaling scheme for density-functional pseudopotential calculations is described in detail. The method is based on a formulation of density functional theory in which the ground state energy is determined by minimization with respect to the density matrix, subject to the condition that the eigenvalues of the latter lie in the range [0,1]. Linear-scaling behavior is achieved by requiring that the density matrix should vanish when the separation of its arguments exceeds a chosen cutoff. The limitation on the eigenvalue range is imposed by the method of Li, Nunes and Vanderbilt. The scheme is implemented by calculating all terms in the energy on a uniform real-space grid, and minimization is performed using the conjugate-gradient method. Tests on a 512-atom Si system show that the total energy converges rapidly as the range of the density matrix is increased. A discussion of the relation between the present method and other linear-scaling methods is given, and some problems that still require solution are indicated.Comment: REVTeX file, 27 pages with 4 uuencoded postscript figure

Three real-space discretization techniques in electronic structure calculations

A characteristic feature of the state-of-the-art of real-space methods in electronic structure calculations is the diversity of the techniques used in the discretization of the relevant partial differential equations. In this context, the main approaches include finite-difference methods, various types of finite-elements and wavelets. This paper reports on the results of several code development projects that approach problems related to the electronic structure using these three different discretization methods. We review the ideas behind these methods, give examples of their applications, and discuss their similarities and differences.Comment: 39 pages, 10 figures, accepted to a special issue of "physica status solidi (b) - basic solid state physics" devoted to the CECAM workshop "State of the art developments and perspectives of real-space electronic structure techniques in condensed matter and molecular physics". v2: Minor stylistic and typographical changes, partly inspired by referee comment

Electronic damping of molecular motion at metal surfaces

A method for the calculation of the damping rate due to electron-hole pair excitation for atomic and molecular motion at metal surfaces is presented. The theoretical basis is provided by Time Dependent Density Functional Theory (TDDFT) in the quasi-static limit and calculations are performed within a standard plane-wave, pseudopotential framework. The artificial periodicity introduced by using a super-cell geometry is removed to derive results for the motion of an isolated atom or molecule, rather than for the coherent motion of an ordered over-layer. The algorithm is implemented in parallel, distributed across both ${\bf k}$ and ${\bf g}$ space, and in a form compatible with the CASTEP code. Test results for the damping of the motion of hydrogen atoms above the Cu(111) surface are presented.Comment: 10 pages, 3 figure

Symmetry-adapted real-space density functional theory for cylindrical geometries: application to large X (X=C, Si, Ge, Sn) nanotubes

We present a symmetry-adapted real-space formulation of Kohn-Sham density functional theory for cylindrical geometries and apply it to the study of large X (X=C, Si, Ge, Sn) nanotubes. Specifically, starting from the Kohn-Sham equations posed on all of space, we reduce the problem to the fundamental domain by incorporating cyclic and periodic symmetries present in the angular and axial directions of the cylinder, respectively. We develop a high-order finite-difference parallel implementation of this formulation, and verify its accuracy against established planewave and real-space codes. Using this implementation, we study the band structure and bending properties of X nanotubes and Xene sheets, respectively. Specifically, we first show that zigzag and armchair X nanotubes with radii in the range 1 to 5 nm are semiconducting. In particular, we find an inverse linear dependence of the bandgap with respect to the radius for all nanotubes, other than the armchair and zigzag type III carbon variants, for which we find an inverse quadratic dependence. Next, we exploit the connection between cyclic symmetry and uniform bending deformations to calculate the bending moduli of Xene sheets in both zigzag and armchair directions. We find Kirchhoff-Love type bending behavior for all sheets, with graphene and stanene possessing the largest and smallest moduli, respectively. In addition, other than graphene, the sheets demonstrate significant anisotropy, with larger bending moduli along the armchair direction. Finally, we demonstrate that the proposed approach has very good parallel scaling and is highly efficient, enabling ab initio simulations of unprecedented size for systems with a high degree of cyclic symmetry. In particular, we show that even micron-sized nanotubes can be simulated with modest computational effort.Comment: 24 pages, 8 figures, 4 table