Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 140, Issue 6, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4864755
Keywords
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Funding
- NSF CAREER award [CHE-0847295]
- NSF SI2-SSI award [OCI-1047696]
- Camille Dreyfus Teacher-Scholar Award
- NSF [CHE-1054286]
- Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0847295] Funding Source: National Science Foundation
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A local density fitting scheme is considered in which atomic orbital (AO) products are approximated using only auxiliary AOs located on one of the nuclei in that product. The possibility of variational collapse to an unphysical attractive electron state that can affect such density fitting [P. Merlot, T. Kjaergaard, T. Helgaker, R. Lindh, F. Aquilante, S. Reine, and T. B. Pedersen, J. Comput. Chem. 34, 1486 (2013)] is alleviated by including atom-wise semidiagonal integrals exactly. Our approach leads to a significant decrease in the computational cost of density fitting for Hartree-Fock theory while still producing results with errors 2-5 times smaller than standard, nonlocal density fitting. Our method allows for large Hartree-Fock and density functional theory computations with exact exchange to be carried out efficiently on large molecules, which we demonstrate by benchmarking our method on 200 of the most widely used prescription drug molecules. Our new fitting scheme leads to smooth and artifact-free potential energy surfaces and the possibility of relatively simple analytic gradients. (C) 2014 AIP Publishing LLC.
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