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Relativistic quantum chemistry: the multiconfigurational approach

Roos, Björn LU and Malmqvist, Per-Åke LU (2004) In Physical Chemistry Chemical Physics 6(11). p.2919-2927
Abstract
A multiconfigurational approach to the quantum chemistry of heavy element compounds is described. Relativistic effects are treated in two steps, both based on the Douglas-Kroll Hamiltonian. Scalar terms are included in the basis set generation and are used to determine wave functions and energies, which include static (through the use of the CASSCF method) and dynamic correlation effects (using multiconfigurational perturbation theory, CASPT2). Spin-orbit coupling is treated in a configuration interaction model, which uses CASSCF wave functions as the basis states. The method is shown to work for all atoms of the periodic system, with the possible exception of the heavier fifth row main group atoms. Illustrative results are presented for... (More)
A multiconfigurational approach to the quantum chemistry of heavy element compounds is described. Relativistic effects are treated in two steps, both based on the Douglas-Kroll Hamiltonian. Scalar terms are included in the basis set generation and are used to determine wave functions and energies, which include static (through the use of the CASSCF method) and dynamic correlation effects (using multiconfigurational perturbation theory, CASPT2). Spin-orbit coupling is treated in a configuration interaction model, which uses CASSCF wave functions as the basis states. The method is shown to work for all atoms of the periodic system, with the possible exception of the heavier fifth row main group atoms. Illustrative results are presented for the main group atoms (spin-orbit splittings), the electronic spectrum of the iridium atom, the ground state of Tl-2 and Pb-2, and for the electronic spectrum of PbO. Some applications in actinide chemistry are also discussed. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
6
issue
11
pages
2919 - 2927
publisher
Royal Society of Chemistry
external identifiers
  • wos:000222357600020
  • scopus:3042764753
ISSN
1463-9084
DOI
10.1039/b401472n
language
English
LU publication?
yes
id
ff843270-9816-4dcb-b719-8c2ddf560ff8 (old id 139633)
date added to LUP
2007-07-17 13:38:52
date last changed
2017-12-10 04:27:57
@article{ff843270-9816-4dcb-b719-8c2ddf560ff8,
  abstract     = {A multiconfigurational approach to the quantum chemistry of heavy element compounds is described. Relativistic effects are treated in two steps, both based on the Douglas-Kroll Hamiltonian. Scalar terms are included in the basis set generation and are used to determine wave functions and energies, which include static (through the use of the CASSCF method) and dynamic correlation effects (using multiconfigurational perturbation theory, CASPT2). Spin-orbit coupling is treated in a configuration interaction model, which uses CASSCF wave functions as the basis states. The method is shown to work for all atoms of the periodic system, with the possible exception of the heavier fifth row main group atoms. Illustrative results are presented for the main group atoms (spin-orbit splittings), the electronic spectrum of the iridium atom, the ground state of Tl-2 and Pb-2, and for the electronic spectrum of PbO. Some applications in actinide chemistry are also discussed.},
  author       = {Roos, Björn and Malmqvist, Per-Åke},
  issn         = {1463-9084},
  language     = {eng},
  number       = {11},
  pages        = {2919--2927},
  publisher    = {Royal Society of Chemistry},
  series       = {Physical Chemistry Chemical Physics},
  title        = {Relativistic quantum chemistry: the multiconfigurational approach},
  url          = {http://dx.doi.org/10.1039/b401472n},
  volume       = {6},
  year         = {2004},
}