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Excitation energies for transition metal atoms - A comparison between coupled cluster methods and second-order perturbation theory

Raab, Juraj LU and Roos, Björn LU (2005) In Advances in Quantum Chemistry 48. p.421-433
Abstract
Coupled cluster methods are compared to multiconfigurational second-order perturbation theory in a study of the high spin d(x)s(2) -> d(x+1)s(1) excitations in first, second, and third row transition metals. Large basis sets of the atomic natural orbital type are used. Scalar relativistic effects are included using the Douglas-Kroll-Hess Hamiltonian. The effect of spin-orbit coupling is demonstrated for third row atoms. The results show that the two methods give results of the same accuracy, with the exception of first row atoms with less than five 3d-electrons. The CASPT2 method here overestimates the effect of 3p correlation with about 0.1 eV.
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Advances in Quantum Chemistry
volume
48
pages
421 - 433
publisher
Elsevier
external identifiers
  • wos:000231014500022
  • scopus:33645885633
ISSN
0065-3276
DOI
10.1016/S0065-3276(05)48022-3
language
English
LU publication?
yes
id
35969626-aeea-4390-b336-bf068d255a71 (old id 152711)
date added to LUP
2007-07-17 13:19:31
date last changed
2017-04-09 04:13:29
@article{35969626-aeea-4390-b336-bf068d255a71,
  abstract     = {Coupled cluster methods are compared to multiconfigurational second-order perturbation theory in a study of the high spin d(x)s(2) -> d(x+1)s(1) excitations in first, second, and third row transition metals. Large basis sets of the atomic natural orbital type are used. Scalar relativistic effects are included using the Douglas-Kroll-Hess Hamiltonian. The effect of spin-orbit coupling is demonstrated for third row atoms. The results show that the two methods give results of the same accuracy, with the exception of first row atoms with less than five 3d-electrons. The CASPT2 method here overestimates the effect of 3p correlation with about 0.1 eV.},
  author       = {Raab, Juraj and Roos, Björn},
  issn         = {0065-3276},
  language     = {eng},
  pages        = {421--433},
  publisher    = {Elsevier},
  series       = {Advances in Quantum Chemistry},
  title        = {Excitation energies for transition metal atoms - A comparison between coupled cluster methods and second-order perturbation theory},
  url          = {http://dx.doi.org/10.1016/S0065-3276(05)48022-3},
  volume       = {48},
  year         = {2005},
}