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Calibration of Cholesky Auxiliary Basis Sets for Multiconfigurational Perturbation Theory Calculations of Excitation Energies

Boström, Jonas LU ; Delcey, Mickael LU ; Aquilante, Francesco; Serrano-Andres, Luis; Pedersen, Thomas Bondo and Lindh, Roland LU (2010) In Journal of Chemical Theory and Computation 6(3). p.747-754
Abstract
The accuracy of auxiliary basis sets derived from Cholesky decomposition of two-electron integrals is assessed for excitation energies calculated at the state-average complete active space self-consistent field (CASSCF) and multiconfigurational second order perturbation theory (CASPT2) levels of theory using segmented as well as generally contracted atomic orbital basis sets. Based on 196 valence excitations in 26 organic molecules and 72 Rydberg excitations in 3 organic molecules, the results show that Cholesky auxiliary basis sets can be used without compromising the accuracy of the multiconfigurational methods. Specifically, with a decomposition threshold of 10(-4) au, the mean error due to the Cholesky auxiliary basis set is 0.001 eV,... (More)
The accuracy of auxiliary basis sets derived from Cholesky decomposition of two-electron integrals is assessed for excitation energies calculated at the state-average complete active space self-consistent field (CASSCF) and multiconfigurational second order perturbation theory (CASPT2) levels of theory using segmented as well as generally contracted atomic orbital basis sets. Based on 196 valence excitations in 26 organic molecules and 72 Rydberg excitations in 3 organic molecules, the results show that Cholesky auxiliary basis sets can be used without compromising the accuracy of the multiconfigurational methods. Specifically, with a decomposition threshold of 10(-4) au, the mean error due to the Cholesky auxiliary basis set is 0.001 eV, or smaller, decreasing with increasing atomic orbital basis set quality. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Theory and Computation
volume
6
issue
3
pages
747 - 754
publisher
The American Chemical Society
external identifiers
  • wos:000275189400014
  • scopus:77950134052
ISSN
1549-9618
DOI
10.1021/ct900612k
language
English
LU publication?
yes
id
abede539-68fd-4e73-8a92-1dba6c8e7f4c (old id 1589553)
date added to LUP
2010-04-20 10:38:51
date last changed
2018-10-03 09:29:15
@article{abede539-68fd-4e73-8a92-1dba6c8e7f4c,
  abstract     = {The accuracy of auxiliary basis sets derived from Cholesky decomposition of two-electron integrals is assessed for excitation energies calculated at the state-average complete active space self-consistent field (CASSCF) and multiconfigurational second order perturbation theory (CASPT2) levels of theory using segmented as well as generally contracted atomic orbital basis sets. Based on 196 valence excitations in 26 organic molecules and 72 Rydberg excitations in 3 organic molecules, the results show that Cholesky auxiliary basis sets can be used without compromising the accuracy of the multiconfigurational methods. Specifically, with a decomposition threshold of 10(-4) au, the mean error due to the Cholesky auxiliary basis set is 0.001 eV, or smaller, decreasing with increasing atomic orbital basis set quality.},
  author       = {Boström, Jonas and Delcey, Mickael and Aquilante, Francesco and Serrano-Andres, Luis and Pedersen, Thomas Bondo and Lindh, Roland},
  issn         = {1549-9618},
  language     = {eng},
  number       = {3},
  pages        = {747--754},
  publisher    = {The American Chemical Society},
  series       = {Journal of Chemical Theory and Computation},
  title        = {Calibration of Cholesky Auxiliary Basis Sets for Multiconfigurational Perturbation Theory Calculations of Excitation Energies},
  url          = {http://dx.doi.org/10.1021/ct900612k},
  volume       = {6},
  year         = {2010},
}