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Main group atoms and dimers studied with a new relativistic ANO basis set

Roos, Björn LU ; Lindh, Roland LU ; Malmqvist, Per-Åke LU ; Veryazov, Valera LU and Widmark, Per-Olof LU (2004) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 108(15). p.2851-2858
Abstract
New basis sets of the atomic natural orbital (ANO) type have been developed for the main group and rare gas atoms. The ANO's 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 dimer at its equilibrium geometry. Scalar relativistic effects are included through the use of a Douglas-Kroll 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 the ground-state potentials for the dimers. These calculations include spin-orbit... (More)
New basis sets of the atomic natural orbital (ANO) type have been developed for the main group and rare gas atoms. The ANO's 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 dimer at its equilibrium geometry. Scalar relativistic effects are included through the use of a Douglas-Kroll 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 the ground-state potentials for the dimers. These calculations include spin-orbit coupling using the RASSCF State Interaction (RASSI-SO) method. The spin-orbit splitting for the lowest atomic term is reproduced with an accuracy of better than 0.05 eV, except for row 5, where it is 0.15 eV. Ionization energies and electron affinities have an accuracy better than 0.2 eV, and atomic polarizabilities for the spherical atoms are computed with errors smaller than 2.5%. Computed bond energies for the dimers are accurate to better than 0.15 eV in most cases (the dimers for row 5 excluded). (Less)
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organization
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type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
108
issue
15
pages
2851 - 2858
publisher
The American Chemical Society
external identifiers
  • wos:000220724300003
  • scopus:2342519355
ISSN
1520-5215
DOI
10.1021/jp031064+
language
English
LU publication?
yes
id
d87c17da-66c7-4e91-a56b-422cb2ecdc0e (old id 139051)
date added to LUP
2007-07-03 16:24:56
date last changed
2017-12-10 04:24:28
@article{d87c17da-66c7-4e91-a56b-422cb2ecdc0e,
  abstract     = {New basis sets of the atomic natural orbital (ANO) type have been developed for the main group and rare gas atoms. The ANO's 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 dimer at its equilibrium geometry. Scalar relativistic effects are included through the use of a Douglas-Kroll 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 the ground-state potentials for the dimers. These calculations include spin-orbit coupling using the RASSCF State Interaction (RASSI-SO) method. The spin-orbit splitting for the lowest atomic term is reproduced with an accuracy of better than 0.05 eV, except for row 5, where it is 0.15 eV. Ionization energies and electron affinities have an accuracy better than 0.2 eV, and atomic polarizabilities for the spherical atoms are computed with errors smaller than 2.5%. Computed bond energies for the dimers are accurate to better than 0.15 eV in most cases (the dimers for row 5 excluded).},
  author       = {Roos, Björn and Lindh, Roland and Malmqvist, Per-Åke and Veryazov, Valera and Widmark, Per-Olof},
  issn         = {1520-5215},
  language     = {eng},
  number       = {15},
  pages        = {2851--2858},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Main group atoms and dimers studied with a new relativistic ANO basis set},
  url          = {http://dx.doi.org/10.1021/jp031064+},
  volume       = {108},
  year         = {2004},
}