Multipole-based integral estimates for the rigorous description of distance dependence in two-electron integrals

• Published in: The Journal of chemical physics Vol. 123; no. 18; p. 184101
• Main Authors: Lambrecht, Daniel S, Ochsenfeld, Christian
• Format: Journal Article
• Language: English
• Published: United States 08.11.2005
• ISSN: 0021-9606
• DOI: 10.1063/1.2079967

We derive multipole-based integral estimates (MBIE) as rigorous and tight upper bounds to four-center two-electron integrals in order to account for the 1/R distance decay between the charge distributions, which is missing in the Schwarz screening commonly used in ab initio methods. Our screening criteria are valid for all angular momenta and can be formulated for any order of multipoles. We have found the expansion limited to dipoles to be sufficiently tight for estimating the integrals in Hartree-Fock and density-functional theories, while the screening effort is negligible. For, e.g., a DNA fragment with 1052 atoms and 10,674 basis functions (6-31G*) the exchange part is faster by a factor of 2.1 as compared to the Schwarz screening both within our linear exchange scheme, whereas a smaller factor of 1.3 is gained for the Coulomb part within the continuous fast multipole method. Most importantly, our new MBIE screening is perfectly suited to exploit the strong distance decay of electron-correlation effects of at least 1/R4 in atomic-orbital-based formulations of correlation methods.