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MiS Preprint

Tensor Numerical Methods in Quantum Chemistry: from Hartree-Fock Energy to Excited States

Venera Khoromskaia and Boris N. Khoromskij


We resume the recent successes of the grid-based tensor numerical methods and discuss their prospects in real-space electronic structure calculations. These methods, based on the low-rank representation of the multidimensional functions and integral operators, first appeared as an accurate tensor calculus for the 3D Hartree potential using 1D complexity operations, and have evolved to entirely grid-based tensor-structured 3D Hartree-Fock eigenvalue solver. It benefits from tensor calculation of the core Hamiltonian and two-electron integrals (TEI) in $O(n\log n)$ complexity using the rank-structured approximation of basis functions, electron densities and convolution integral operators all represented on 3D $n\times n\times n $ Cartesian grids. The algorithm for calculating TEI tensor in a form of the Cholesky decomposition is based on multiple factorizations using algebraic 1D "density fitting" scheme , which yield an almost irreducible number of product basis functions involved in the $3$D convolution integrals, depending on a threshold $\varepsilon >0$.

The basis functions are not restricted to separable Gaussians, since the analytical integration is substituted by high-precision tensor-structured numerical quadratures. The tensor approaches to post-Hartree-Fock calculations for the MP2 energy correction and for the Bethe-Salpeter excited states, based on using low-rank factorizations and the reduced basis method, were recently introduced. Another direction is related to the recent attempts to develop a tensor-based Hartree-Fock numerical scheme for finite lattice-structured systems, where one of the numerical challenges is the summation of electrostatic potentials of a large number of nuclei. The 3D grid-based tensor method for calculation of a potential sum on a $L\times L\times L$ lattice manifests the linear in $L$ computational work, $O(L)$, instead of the usual $O(L^3 \log L)$ scaling by the Ewald-type approaches. The accuracy of the order of atomic radii, $ h\sim 10^{-4} Å$, for the grid representation of electrostatic potentials is achieved due to low cost of using $1$D operations on large 3D grids.

Mar 3, 2015
Mar 4, 2015
MSC Codes:
65F30, 65F50, 65N35, 65F10
Electronic structure calculations, Two-electron integrals, multidimensional integrals, tensor decompositions, quantized tensor approximation, low-rank Cholesky factorization, Hartree-Fock solver, lattice potential sums

Related publications

2015 Journal Open Access
Venera Khoromskaia and Boris N. Khoromskij

Tensor numerical methods in quantum chemistry : from Hartree-Fock to excitation energies

In: Physical chemistry, chemical physics, 17 (2015) 47, pp. 31491-31509