Skip to main content

Lund University Publications

LUND UNIVERSITY LIBRARIES

Cholesky decomposition-based multiconfiguration second-order perturbation theory (CD-CASPT2): Application to the spin-state energetics of Co-III(diiminato)(NPh)

Aquilante, Francesco LU ; Malmqvist, Per-Åke LU ; Pedersen, Thomas LU ; Ghosh, Abhik and Roos, Björn LU (2008) In Journal of Chemical Theory and Computation 4(5). p.694-702
Abstract
The electronic structure and low-lying electronic states of a Co-III(diiminato)(NPh) complex have been studied using mulficonfigurational wave function theory (CASSCF/CASPT2) The results have been compared to those obtained with density functional theory. The best agreement with ab initio results is obtained with a modified B3LYP functional containing a reduced amount (15%) of Hartree-Fock exchange. A relativistic basis set with 869 functions has been employed in the most extensive ab initio calculations, where a Cholesky decomposition technique was used to overcome problems arising from the large size of the two-electron integral matrix. It is shown that this approximation reproduces results obtained with the full integral set to a high... (More)
The electronic structure and low-lying electronic states of a Co-III(diiminato)(NPh) complex have been studied using mulficonfigurational wave function theory (CASSCF/CASPT2) The results have been compared to those obtained with density functional theory. The best agreement with ab initio results is obtained with a modified B3LYP functional containing a reduced amount (15%) of Hartree-Fock exchange. A relativistic basis set with 869 functions has been employed in the most extensive ab initio calculations, where a Cholesky decomposition technique was used to overcome problems arising from the large size of the two-electron integral matrix. It is shown that this approximation reproduces results obtained with the full integral set to a high accuracy, thus opening the possibility to use this approach to perform multiconfigurational wave-function-based quantum chemistry on much larger systems relative to what has been possible until now. (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
4
issue
5
pages
694 - 702
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000255802700003
  • scopus:47349098168
  • pmid:26621084
ISSN
1549-9618
DOI
10.1021/ct700263h
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
f52730a1-f710-4e44-87e0-afcddd030ef5 (old id 1203690)
date added to LUP
2016-04-01 11:49:17
date last changed
2025-04-04 14:40:33
@article{f52730a1-f710-4e44-87e0-afcddd030ef5,
  abstract     = {{The electronic structure and low-lying electronic states of a Co-III(diiminato)(NPh) complex have been studied using mulficonfigurational wave function theory (CASSCF/CASPT2) The results have been compared to those obtained with density functional theory. The best agreement with ab initio results is obtained with a modified B3LYP functional containing a reduced amount (15%) of Hartree-Fock exchange. A relativistic basis set with 869 functions has been employed in the most extensive ab initio calculations, where a Cholesky decomposition technique was used to overcome problems arising from the large size of the two-electron integral matrix. It is shown that this approximation reproduces results obtained with the full integral set to a high accuracy, thus opening the possibility to use this approach to perform multiconfigurational wave-function-based quantum chemistry on much larger systems relative to what has been possible until now.}},
  author       = {{Aquilante, Francesco and Malmqvist, Per-Åke and Pedersen, Thomas and Ghosh, Abhik and Roos, Björn}},
  issn         = {{1549-9618}},
  language     = {{eng}},
  number       = {{5}},
  pages        = {{694--702}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of Chemical Theory and Computation}},
  title        = {{Cholesky decomposition-based multiconfiguration second-order perturbation theory (CD-CASPT2): Application to the spin-state energetics of Co-III(diiminato)(NPh)}},
  url          = {{http://dx.doi.org/10.1021/ct700263h}},
  doi          = {{10.1021/ct700263h}},
  volume       = {{4}},
  year         = {{2008}},
}