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New relativistic ANO basis sets for transition metal atoms

Roos, Björn LU ; Lindh, Roland LU ; Malmqvist, Per-Åke LU ; Veryazov, Valera LU and Widmark, Per-Olof LU (2005) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 109(29). p.6575-6579
Abstract
New basis sets of the atomic natural orbital (ANO) type have been developed for the first, second, and third row transition metal atoms. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive and negative ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies, electron affinities, and excitation energies for all atoms and polarizabilities for spherically symmetric atoms. These... (More)
New basis sets of the atomic natural orbital (ANO) type have been developed for the first, second, and third row transition metal atoms. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive and negative ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies, electron affinities, and excitation energies for all atoms and polarizabilities for spherically symmetric atoms. These calculations include spin-orbit coupling using a variation-perturbation approach. Computed ionization energies have an accuracy better than 0.2 eV in most cases. The accuracy of computed electron affinities is the same except in cases where the experimental values are smaller than 0.5 eV. Accurate results are obtained for the polarizabilities of atoms with spherical symmetry. Multiplet levels are presented for some of the third row transition metals. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
109
issue
29
pages
6575 - 6579
publisher
The American Chemical Society
external identifiers
  • wos:000230696000023
  • scopus:23844490530
ISSN
1520-5215
DOI
10.1021/jp0581126
language
English
LU publication?
yes
id
d2e9b947-0135-44b5-9ecc-c9595392af44 (old id 152720)
date added to LUP
2007-07-17 13:36:18
date last changed
2017-11-19 04:05:32
@article{d2e9b947-0135-44b5-9ecc-c9595392af44,
  abstract     = {New basis sets of the atomic natural orbital (ANO) type have been developed for the first, second, and third row transition metal atoms. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive and negative ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies, electron affinities, and excitation energies for all atoms and polarizabilities for spherically symmetric atoms. These calculations include spin-orbit coupling using a variation-perturbation approach. Computed ionization energies have an accuracy better than 0.2 eV in most cases. The accuracy of computed electron affinities is the same except in cases where the experimental values are smaller than 0.5 eV. Accurate results are obtained for the polarizabilities of atoms with spherical symmetry. Multiplet levels are presented for some of the third row transition metals.},
  author       = {Roos, Björn and Lindh, Roland and Malmqvist, Per-Åke and Veryazov, Valera and Widmark, Per-Olof},
  issn         = {1520-5215},
  language     = {eng},
  number       = {29},
  pages        = {6575--6579},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {New relativistic ANO basis sets for transition metal atoms},
  url          = {http://dx.doi.org/10.1021/jp0581126},
  volume       = {109},
  year         = {2005},
}