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

TL;DR

This paper reviews tensor numerical methods in quantum chemistry, highlighting their efficiency in real-space calculations, including Hartree-Fock, post-Hartree-Fock, and lattice systems, with significant reductions in computational complexity.

Contribution

It introduces tensor-based algorithms for electronic structure calculations that significantly improve computational efficiency and extend applicability to excited states and lattice systems.

Findings

Tensor methods achieve $O(n \, log n)$ complexity for core Hamiltonian and TEI calculations.

Tensor approaches enable linear $O(L)$ scaling for potential sums on lattice structures.

Tensor algorithms facilitate accurate and efficient post-Hartree-Fock and excited state computations.

Abstract

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, led 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. 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.