Main group atoms and dimers studied with a new relativistic ANO basis set
(2004) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 108(15). p.28512858 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 DouglasKroll Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using secondorder perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies, electron affinities, and excitation energies for all atoms and the groundstate potentials for the dimers. These calculations include spinorbit... (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 DouglasKroll Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using secondorder perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies, electron affinities, and excitation energies for all atoms and the groundstate potentials for the dimers. These calculations include spinorbit coupling using the RASSCF State Interaction (RASSISO) method. The spinorbit 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)
Please use this url to cite or link to this publication:
http://lup.lub.lu.se/record/139051
 author
 Roos, Björn ^{LU} ; Lindh, Roland ^{LU} ; Malmqvist, PerÅke ^{LU} ; Veryazov, Valera ^{LU} and Widmark, PerOlof ^{LU}
 organization
 publishing date
 2004
 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
 15205215
 DOI
 10.1021/jp031064+
 language
 English
 LU publication?
 yes
 id
 d87c17da66c74e91a56b422cb2ecdc0e (old id 139051)
 date added to LUP
 20070703 16:24:56
 date last changed
 20171210 04:24:28
@article{d87c17da66c74e91a56b422cb2ecdc0e, 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 DouglasKroll Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using secondorder perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies, electron affinities, and excitation energies for all atoms and the groundstate potentials for the dimers. These calculations include spinorbit coupling using the RASSCF State Interaction (RASSISO) method. The spinorbit 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, PerÅke and Veryazov, Valera and Widmark, PerOlof}, issn = {15205215}, language = {eng}, number = {15}, pages = {28512858}, 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}, }