Skip to main content

Lund University Publications

LUND UNIVERSITY LIBRARIES

Analytical Gradients of Hartree-Fock Exchange with Density Fitting Approximations

Boström, Jonas LU ; Aquilante, Francesco ; Pedersen, Thomas Bondo and Lindh, Roland (2013) In Journal of Chemical Theory and Computation 9(1). p.204-212
Abstract
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 degrees, and 0.5 degrees, respectively. The overall speedup of geometry optimizations is about 1 order of magnitude... (More)
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 degrees, and 0.5 degrees, 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. (Less)
Please use this url to cite or link to this publication:
author
; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Theory and Computation
volume
9
issue
1
pages
204 - 212
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000313378700024
  • scopus:84872128446
  • pmid:26589023
ISSN
1549-9618
DOI
10.1021/ct200836x
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
id
e7f6660a-4b86-4121-a18f-6e23d22e10d8 (old id 3590861)
date added to LUP
2016-04-01 10:57:44
date last changed
2023-01-02 17:27:55
@article{e7f6660a-4b86-4121-a18f-6e23d22e10d8,
  abstract     = {{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 degrees, and 0.5 degrees, 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.}},
  author       = {{Boström, Jonas and Aquilante, Francesco and Pedersen, Thomas Bondo and Lindh, Roland}},
  issn         = {{1549-9618}},
  language     = {{eng}},
  number       = {{1}},
  pages        = {{204--212}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of Chemical Theory and Computation}},
  title        = {{Analytical Gradients of Hartree-Fock Exchange with Density Fitting Approximations}},
  url          = {{http://dx.doi.org/10.1021/ct200836x}},
  doi          = {{10.1021/ct200836x}},
  volume       = {{9}},
  year         = {{2013}},
}