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Calculation of EPR g tensors for transition-metal complexes based on multiconfigurational perturbation theory (CASPT2)

Vancoillie, Steven ; Malmqvist, Per-Åke LU and Pierloot, Kristine (2007) In ChemPhysChem 8(12). p.1803-1815
Abstract
The computation of the electronic g tensor by two multireference methods is presented and applied to a selection of molecules including CN, BO, AIO, GaO, InO, ZnH, ZnF, O-2, H2O+, O-3(-), and H2CO+ (group A) as well as TiF3, CuCl42-, Cu(NH3)(4)(2+) and a series of d(1)-MOX4n- compounds, with M = V Cr, Mo, Tc, W, Re and X = F Cl, Br (group B). Two approaches are considered, namely, one in which spin-orbit coupling and the Zeeman effect are included using second-order perturbation theory and another one in which the Zeeman effect is added through first-order degenerate perturbation theory within the ground-state Kramers doublet. The two methods have been implemented into the MOLCAS quantum chemistry software package. The results obtained for... (More)
The computation of the electronic g tensor by two multireference methods is presented and applied to a selection of molecules including CN, BO, AIO, GaO, InO, ZnH, ZnF, O-2, H2O+, O-3(-), and H2CO+ (group A) as well as TiF3, CuCl42-, Cu(NH3)(4)(2+) and a series of d(1)-MOX4n- compounds, with M = V Cr, Mo, Tc, W, Re and X = F Cl, Br (group B). Two approaches are considered, namely, one in which spin-orbit coupling and the Zeeman effect are included using second-order perturbation theory and another one in which the Zeeman effect is added through first-order degenerate perturbation theory within the ground-state Kramers doublet. The two methods have been implemented into the MOLCAS quantum chemistry software package. The results obtained for the molecules in group A are in good agreement with experiment and with previously reported calculated g values. The results for the molecules in group B vary. While the g values for the d(1) systems are superior to previous theoretical results, those obtained for the d(9) systems are too large compared to the experimental values. (Less)
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author
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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
EPR, electronic structure, ab initio calculations, computer chemistry, transition metals, spectroscopy
in
ChemPhysChem
volume
8
issue
12
pages
1803 - 1815
publisher
John Wiley & Sons Inc.
external identifiers
  • wos:000249602300011
  • scopus:34548433333
ISSN
1439-7641
DOI
10.1002/cphc.200700128
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
id
91b5a60c-0d56-4099-b3b6-58fd57636214 (old id 656686)
date added to LUP
2016-04-01 12:05:43
date last changed
2023-01-03 03:46:28
@article{91b5a60c-0d56-4099-b3b6-58fd57636214,
  abstract     = {{The computation of the electronic g tensor by two multireference methods is presented and applied to a selection of molecules including CN, BO, AIO, GaO, InO, ZnH, ZnF, O-2, H2O+, O-3(-), and H2CO+ (group A) as well as TiF3, CuCl42-, Cu(NH3)(4)(2+) and a series of d(1)-MOX4n- compounds, with M = V Cr, Mo, Tc, W, Re and X = F Cl, Br (group B). Two approaches are considered, namely, one in which spin-orbit coupling and the Zeeman effect are included using second-order perturbation theory and another one in which the Zeeman effect is added through first-order degenerate perturbation theory within the ground-state Kramers doublet. The two methods have been implemented into the MOLCAS quantum chemistry software package. The results obtained for the molecules in group A are in good agreement with experiment and with previously reported calculated g values. The results for the molecules in group B vary. While the g values for the d(1) systems are superior to previous theoretical results, those obtained for the d(9) systems are too large compared to the experimental values.}},
  author       = {{Vancoillie, Steven and Malmqvist, Per-Åke and Pierloot, Kristine}},
  issn         = {{1439-7641}},
  keywords     = {{EPR; electronic structure; ab initio calculations; computer chemistry; transition metals; spectroscopy}},
  language     = {{eng}},
  number       = {{12}},
  pages        = {{1803--1815}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{ChemPhysChem}},
  title        = {{Calculation of EPR g tensors for transition-metal complexes based on multiconfigurational perturbation theory (CASPT2)}},
  url          = {{http://dx.doi.org/10.1002/cphc.200700128}},
  doi          = {{10.1002/cphc.200700128}},
  volume       = {{8}},
  year         = {{2007}},
}