Preprint 29/2009

Canonical tensor products as a generalization of Gaussian-type orbitals

Sambasiva Rao Chinnamsetty, Mike Espig, Heinz-Jürgen Flad, and Wolfgang Hackbusch

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Submission date: 08. Jul. 2009
Pages: 16
published as: Canonical tensor products as a generalization of Gaussian-type orbitals.
In: Progress in physical chemistry 3 : modern and universal first-principles methods for many-electron systems in chemistry and physics / M. Dolg (ed.)
München : Oldenbourg-Verlag, 2010. - P. 391 - 404 
published as: Canonical tensor products as a generalization of Gaussian-type orbitals.
In: Zeitschrift für physikalische Chemie, 224 (2010) 3/4, p. 681-694 
DOI number (of the published article): 10.1524/zpch.2010.6131
Bibtex
Keywords and phrases: Tensor product approximation, Density-fitting method, Orbital products, Two-electron integrals, Pseudopotentials, Hartree-Fock energy
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Abstract:
We propose a possible generalization of Gaussian-type orbital (GTO) bases by means of canonical tensor products. The present work focus on the application of tensor product as an alternative to conventional GTO based density fitting schemes. Tensor product approximation leads to highly nonlinear optimization problems which require sophisticated algorithms. We give a brief description of the optimization problem and algorithm. The present work extends our previous paper [S. R. Chinnamsetty, M. Espig, B. N. Khoromskij, W. Hackbusch and H.-J. Flad, J. Chem. Phys. 127 (2007), 084110], where we discussed tensor product approximations of the electron density and the Hartree potential, to orbital products which are required for the exchange part of Hartree-Fock and in post Hartree-Fock methods. We provide a detailed error analysis for the Coulomb and exchange terms in Hartree-Fock calculations. Furthermore, a comparison is given between all-electron and pseudopotential calculations.

18.07.2014, 01:42