A Novel Method for the Solution of the Schroedinger Eq. in the Presence of Exchange Terms

In the Hartree-Fock approximation the Pauli exclusion principle leads to a Schroedinger Eq. of an integro-differential form. We describe a new spectral noniterative method (S-IEM), previously developed for solving the Lippman-Schwinger integral equation with local potentials, which has now been extended so as to include the exchange nonlocality. We apply it to the restricted case of electron-Hydrogen scattering in which the bound electron remains in the ground state and the incident electron has zero angular momentum, and we compare the acuracy and economy of the new method to three other methods. One is a non-iterative solution (NIEM) of the integral equation as described by Sams and Kouri in 1969. Another is an iterative method introduced by Kim and Udagawa in 1990 for nuclear physics applications, which makes an expansion of the solution into an especially favorable basis obtained by a method of moments. The third one is based on the Singular Value Decomposition of the exchange term followed by iterations over the remainder. The S-IEM method turns out to be more accurate by many orders of magnitude than any of the other three methods described above for the same number of mesh points.Comment: 29 pages, 4 figures, submitted to Phys. Rev.

A fast semi-direct least squares algorithm for hierarchically block separable matrices

We present a fast algorithm for linear least squares problems governed by hierarchically block separable (HBS) matrices. Such matrices are generally dense but data-sparse and can describe many important operators including those derived from asymptotically smooth radial kernels that are not too oscillatory. The algorithm is based on a recursive skeletonization procedure that exposes this sparsity and solves the dense least squares problem as a larger, equality-constrained, sparse one. It relies on a sparse QR factorization coupled with iterative weighted least squares methods. In essence, our scheme consists of a direct component, comprised of matrix compression and factorization, followed by an iterative component to enforce certain equality constraints. At most two iterations are typically required for problems that are not too ill-conditioned. For an $M \times N$ HBS matrix with $M \geq N$ having bounded off-diagonal block rank, the algorithm has optimal $\mathcal{O} (M + N)$ complexity. If the rank increases with the spatial dimension as is common for operators that are singular at the origin, then this becomes $\mathcal{O} (M + N)$ in 1D, $\mathcal{O} (M + N^{3/2})$ in 2D, and $\mathcal{O} (M + N^{2})$ in 3D. We illustrate the performance of the method on both over- and underdetermined systems in a variety of settings, with an emphasis on radial basis function approximation and efficient updating and downdating.Comment: 24 pages, 8 figures, 6 tables; to appear in SIAM J. Matrix Anal. App

Rapid evaluation of radial basis functions

Over the past decade, the radial basis function method has been shown to produce high quality solutions to the multivariate scattered data interpolation problem. However, this method has been associated with very high computational cost, as compared to alternative methods such as finite element or multivariate spline interpolation. For example. the direct evaluation at M locations of a radial basis function interpolant with N centres requires O(M N) floating-point operations. In this paper we introduce a fast evaluation method based on the Fast Gauss Transform and suitable quadrature rules. This method has been applied to the Hardy multiquadric, the inverse multiquadric and the thin-plate spline to reduce the computational complexity of the interpolant evaluation to O(M + N) floating point operations. By using certain localisation properties of conditionally negative definite functions this method has several performance advantages against traditional hierarchical rapid summation methods which we discuss in detail

Application of Fredholm integral equations inverse theory to the radial basis function approximation problem

This paper reveals and examines the relationship between the solution and stability of Fredholm integral equations and radial basis function approximation or interpolation. The underlying system (kernel) matrices are shown to have a smoothing property which is dependent on the choice of kernel. Instead of using the condition number to describe the ill-conditioning, hence only looking at the largest and smallest singular values of the matrix, techniques from inverse theory, particularly the Picard condition, show that it is understanding the exponential decay of the singular values which is critical for interpreting and mitigating instability. Results on the spectra of certain classes of kernel matrices are reviewed, verifying the exponential decay of the singular values. Numerical results illustrating the application of integral equation inverse theory are also provided and demonstrate that interpolation weights may be regarded as samplings of a weighted solution of an integral equation. This is then relevant for mapping from one set of radial basis function centers to another set. Techniques for the solution of integral equations can be further exploited in future studies to find stable solutions and to reduce the impact of errors in the data

A new approach for solving nonlinear Thomas-Fermi equation based on fractional order of rational Bessel functions

In this paper, the fractional order of rational Bessel functions collocation method (FRBC) to solve Thomas-Fermi equation which is defined in the semi-infinite domain and has singularity at $x = 0$ and its boundary condition occurs at infinity, have been introduced. We solve the problem on semi-infinite domain without any domain truncation or transformation of the domain of the problem to a finite domain. This approach at first, obtains a sequence of linear differential equations by using the quasilinearization method (QLM), then at each iteration solves it by FRBC method. To illustrate the reliability of this work, we compare the numerical results of the present method with some well-known results in other to show that the new method is accurate, efficient and applicable

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