Analytical Gradients of Hartree–Fock Exchange with Density Fitting Approximations

We extend the local exchange (LK) algorithm [Aquilante, F.; Pedersen, T. B.; Lindh, R. J. Chem. Phys. 2007, 126, 194106] to the calculation of analytical gradients with density fitting. We discuss the features of the screening procedure and demonstrate the possible advantages of using this formulati...

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Published inJournal of chemical theory and computation Vol. 9; no. 1; pp. 204 - 212
Main Authors Boström, Jonas, Aquilante, Francesco, Pedersen, Thomas Bondo, Lindh, Roland
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 08.01.2013
Subjects
Chemical Sciences
Kemi
Natural Sciences
Naturvetenskap
Teoretisk kemi
Theoretical Chemistry
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Summary:We extend the local exchange (LK) algorithm [Aquilante, F.; Pedersen, T. B.; Lindh, R. J. Chem. Phys. 2007, 126, 194106] to the calculation of analytical gradients with density fitting. We discuss the features of the screening procedure and demonstrate the possible advantages of using this formulation, which is easily interfaced to a standard integral-direct gradient code. With auxiliary basis sets obtained from Cholesky decomposition of atomic or molecular integral blocks with a decomposition threshold of 10–4 E h , typical errors due to the density fitting in bond lengths, bond angles, and dihedral angles are 0.1 pm, 0.1°, and 0.5°, respectively. The overall speedup of geometry optimizations is about 1 order of magnitude for atomic natural-orbital-type basis sets but much less pronounced for correlation-consistent basis sets.
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ISSN:1549-9618
1549-9626
1549-9626
DOI:10.1021/ct200836x