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Coupled Cluster and Moller-Plesset Perturbation Theory Calculations of Noncovalent Intermolecular Interactions using Density Fitting with Auxiliary Basis Sets from Cholesky Decompositions

Boström, Jonas LU ; Pitonak, Michal; Aquilante, Francesco; Neogrady, Pavel; Pedersen, Thomas Bondo and Lindh, Roland (2012) In Journal of Chemical Theory and Computation 8(6). p.1921-1928
Abstract
We compute noncovalent intermolecular interaction energies for the S22 test set [Phys. Chem. Chem. Phys. 2006, 8, 1985-1993] of molecules at the Moller-Plesset and coupled cluster levels of supermolecular theory using density fitting (DF) to approximate all two-electron integrals. The error due to the DF approximation is analyzed for a range of auxiliary basis sets derived from Cholesky decomposition (CD) in conjunction with correlation consistent and atomic natural orbital valence basis sets. A Cholesky decomposition threshold of 10(-4)E(h) for full molecular CD and its one-center approximation (1C-CD) generally yields errors below 0.03 kcal/mol, whereas 10(-3)E(h) is sufficient to obtain the same level of accuracy or better with the... (More)
We compute noncovalent intermolecular interaction energies for the S22 test set [Phys. Chem. Chem. Phys. 2006, 8, 1985-1993] of molecules at the Moller-Plesset and coupled cluster levels of supermolecular theory using density fitting (DF) to approximate all two-electron integrals. The error due to the DF approximation is analyzed for a range of auxiliary basis sets derived from Cholesky decomposition (CD) in conjunction with correlation consistent and atomic natural orbital valence basis sets. A Cholesky decomposition threshold of 10(-4)E(h) for full molecular CD and its one-center approximation (1C-CD) generally yields errors below 0.03 kcal/mol, whereas 10(-3)E(h) is sufficient to obtain the same level of accuracy or better with the atomic CD (aCD) and atomic compact CD (acCD) auxiliary basis sets. Comparing to commonly used predefined auxiliary basis sets, we find that while the aCD and acCD sets are larger by a factor of 2-4 with triple-zeta AO basis sets, they provide results 1-2 orders of magnitude more accurate. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Theory and Computation
volume
8
issue
6
pages
1921 - 1928
publisher
The American Chemical Society
external identifiers
  • wos:000305092400007
  • scopus:84862223271
ISSN
1549-9618
DOI
10.1021/ct30030181
language
English
LU publication?
yes
id
4be4ac30-3d42-4daf-9a60-1815eaa71a02 (old id 2892327)
date added to LUP
2012-07-26 10:14:22
date last changed
2017-11-05 03:07:08
@article{4be4ac30-3d42-4daf-9a60-1815eaa71a02,
  abstract     = {We compute noncovalent intermolecular interaction energies for the S22 test set [Phys. Chem. Chem. Phys. 2006, 8, 1985-1993] of molecules at the Moller-Plesset and coupled cluster levels of supermolecular theory using density fitting (DF) to approximate all two-electron integrals. The error due to the DF approximation is analyzed for a range of auxiliary basis sets derived from Cholesky decomposition (CD) in conjunction with correlation consistent and atomic natural orbital valence basis sets. A Cholesky decomposition threshold of 10(-4)E(h) for full molecular CD and its one-center approximation (1C-CD) generally yields errors below 0.03 kcal/mol, whereas 10(-3)E(h) is sufficient to obtain the same level of accuracy or better with the atomic CD (aCD) and atomic compact CD (acCD) auxiliary basis sets. Comparing to commonly used predefined auxiliary basis sets, we find that while the aCD and acCD sets are larger by a factor of 2-4 with triple-zeta AO basis sets, they provide results 1-2 orders of magnitude more accurate.},
  author       = {Boström, Jonas and Pitonak, Michal and Aquilante, Francesco and Neogrady, Pavel and Pedersen, Thomas Bondo and Lindh, Roland},
  issn         = {1549-9618},
  language     = {eng},
  number       = {6},
  pages        = {1921--1928},
  publisher    = {The American Chemical Society},
  series       = {Journal of Chemical Theory and Computation},
  title        = {Coupled Cluster and Moller-Plesset Perturbation Theory Calculations of Noncovalent Intermolecular Interactions using Density Fitting with Auxiliary Basis Sets from Cholesky Decompositions},
  url          = {http://dx.doi.org/10.1021/ct30030181},
  volume       = {8},
  year         = {2012},
}