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Analytical Gradients of the Second-Order Moller-Plesset Energy Using Cholesky Decompositions

Boström, Jonas LU ; Veryazov, Valera LU ; Aquilante, Francesco; Pedersen, Thomas Bondo and Lindh, Roland (2014) In International Journal of Quantum Chemistry 114(5). p.321-327
Abstract
An algorithm for computing analytical gradients of the second-order MOller-Plesset (MP2) energy using density fitting (DF) is presented. The algorithm assumes that the underlying canonical Hartree-Fock reference is obtained with the same auxiliary basis set, which we obtain by Cholesky decomposition (CD) of atomic electron repulsion integrals. CD is also used for the negative semidefinite MP2 amplitude matrix. Test calculations on the weakly interacting dimers of the S22 test set (Jureka et al., Phys. Chem. Chem. Phys. 2006, 8, 1985) show that the geometry errors due to the auxiliary basis set are negligible. With double-zeta basis sets, the error due to the DF approximation in intermolecular bond lengths is better than 0.1 pm. The... (More)
An algorithm for computing analytical gradients of the second-order MOller-Plesset (MP2) energy using density fitting (DF) is presented. The algorithm assumes that the underlying canonical Hartree-Fock reference is obtained with the same auxiliary basis set, which we obtain by Cholesky decomposition (CD) of atomic electron repulsion integrals. CD is also used for the negative semidefinite MP2 amplitude matrix. Test calculations on the weakly interacting dimers of the S22 test set (Jureka et al., Phys. Chem. Chem. Phys. 2006, 8, 1985) show that the geometry errors due to the auxiliary basis set are negligible. With double-zeta basis sets, the error due to the DF approximation in intermolecular bond lengths is better than 0.1 pm. The computational time is typically reduced by a factor of 6-7. (c) 2013 Wiley Periodicals, Inc. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Cholesky decomposition, density fitting, MP2, analytic gradients
in
International Journal of Quantum Chemistry
volume
114
issue
5
pages
321 - 327
publisher
John Wiley & Sons
external identifiers
  • wos:000329794400003
  • scopus:84892881435
ISSN
0020-7608
DOI
10.1002/qua.24563
language
English
LU publication?
yes
id
2cc64586-11d2-4e42-bb37-ea1408c2321f (old id 4318828)
date added to LUP
2014-02-25 13:10:42
date last changed
2017-09-17 04:01:18
@article{2cc64586-11d2-4e42-bb37-ea1408c2321f,
  abstract     = {An algorithm for computing analytical gradients of the second-order MOller-Plesset (MP2) energy using density fitting (DF) is presented. The algorithm assumes that the underlying canonical Hartree-Fock reference is obtained with the same auxiliary basis set, which we obtain by Cholesky decomposition (CD) of atomic electron repulsion integrals. CD is also used for the negative semidefinite MP2 amplitude matrix. Test calculations on the weakly interacting dimers of the S22 test set (Jureka et al., Phys. Chem. Chem. Phys. 2006, 8, 1985) show that the geometry errors due to the auxiliary basis set are negligible. With double-zeta basis sets, the error due to the DF approximation in intermolecular bond lengths is better than 0.1 pm. The computational time is typically reduced by a factor of 6-7. (c) 2013 Wiley Periodicals, Inc.},
  author       = {Boström, Jonas and Veryazov, Valera and Aquilante, Francesco and Pedersen, Thomas Bondo and Lindh, Roland},
  issn         = {0020-7608},
  keyword      = {Cholesky decomposition,density fitting,MP2,analytic gradients},
  language     = {eng},
  number       = {5},
  pages        = {321--327},
  publisher    = {John Wiley & Sons},
  series       = {International Journal of Quantum Chemistry},
  title        = {Analytical Gradients of the Second-Order Moller-Plesset Energy Using Cholesky Decompositions},
  url          = {http://dx.doi.org/10.1002/qua.24563},
  volume       = {114},
  year         = {2014},
}