Preprint 44/2009

Numerical solution of the Hartree-Fock equation in multilevel tensor-structured format

Boris N. Khoromskij, Venera Khoromskaia,and Heinz-Jürgen Flad

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Submission date: 24. Jul. 2009 (revised version: October 2010)
Pages: 26
published in: SIAM journal on scientific computing, 33 (2011) 1, p. 45-65 
DOI number (of the published article): 10.1137/090777372
MSC-Numbers: 65F30, 65F50, 65N35, 65F10
Keywords and phrases: Hartree-Fock equation, Tucker/canonical models, discrete multivariate convolution, Tensor-truncated methods, multilevel SCF iteration
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In this paper, we describe a novel method for robust and accurate iterative solution of the self-consistent Hartree-Fock equation in formula10 based on the idea of tensor-structured computation of the electron density and the nonlinear Hartree and (nonlocal) exchange operators at all steps of the iterative process. We apply the self-consistent field (SCF) iteration to the Galerkin discretisation in a set of low separation rank basis functions that are solely specified by the respective values on a 3D Cartesian grid. The approximation error is estimated by formula12, where formula14 is the mesh size of formula16 tensor grid, while the numerical complexity to compute the Galerkin matrices scales linearly in formula18. We propose the tensor-truncated version of the SCF iteration using the traditional direct inversion in the iterative subspace (DIIS) scheme enhanced by the multilevel acceleration with the grid dependent termination criteria at each discretization level. This implies that the overall computational cost scales almost linearly in the univariate problem size n. Numerical illustrations are presented for the all electron case of Hformula22O, and pseudopotential case of CHformula24 and CHformula26OH molecules. The proposed scheme is not restricted to a priori given rank-1 basis sets allowing analytically integrable convolution transform with the Newton kernel, that opens further perspectives for promotion of the tensor-structured methods in computational quantum chemistry.

07.10.2017, 01:41