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Attractive electron-electron interactions within robust local fitting approximations
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.ORCID iD: 0000-0001-7567-8295
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2013 (English)In: Journal of Computational Chemistry, ISSN 0192-8651, E-ISSN 1096-987X, Vol. 34, no 17, 1486-1496 p.Article in journal (Refereed) Published
Abstract [en]

An analysis of Dunlap's robust fitting approach reveals that the resulting two-electron integral matrix is not manifestly positive semidefinite when local fitting domains or non-Coulomb fitting metrics are used. We present a highly local approximate method for evaluating four-center two-electron integrals based on the resolution-of-the-identity (RI) approximation and apply it to the construction of the Coulomb and exchange contributions to the Fock matrix. In this pair-atomic resolution-of-the-identity (PARI) approach, atomic-orbital (AO) products are expanded in auxiliary functions centered on the two atoms associated with each product. Numerical tests indicate that in 1% or less of all HartreeFock and KohnSham calculations, the indefinite integral matrix causes nonconvergence in the self-consistent-field iterations. In these cases, the two-electron contribution to the total energy becomes negative, meaning that the electronic interaction is effectively attractive, and the total energy is dramatically lower than that obtained with exact integrals. In the vast majority of our test cases, however, the indefiniteness does not interfere with convergence. The total energy accuracy is comparable to that of the standard Coulomb-metric RI method. The speed-up compared with conventional algorithms is similar to the RI method for Coulomb contributions; exchange contributions are accelerated by a factor of up to eight with a triple-zeta quality basis set. A positive semidefinite integral matrix is recovered within PARI by introducing local auxiliary basis functions spanning the full AO product space, as may be achieved by using Cholesky-decomposition techniques. Local completion, however, slows down the algorithm to a level comparable with or below conventional calculations. 

Place, publisher, year, edition, pages
2013. Vol. 34, no 17, 1486-1496 p.
Keyword [en]
resolution-of-the-identity, density fitting, indefinite two-electron integral matrix, convergence problems, HartreeFock, density-functional theory
National Category
Natural Sciences
URN: urn:nbn:se:uu:diva-202890DOI: 10.1002/jcc.23284ISI: 000319404800006OAI: diva2:634678
Available from: 2013-07-01 Created: 2013-07-01 Last updated: 2015-01-08Bibliographically approved

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Lindh, RolandAquilante, Francesco
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