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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
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
external identifiers
  • wos:000249602300011
  • scopus:34548433333
ISSN
1439-7641
DOI
10.1002/cphc.200700128
language
English
LU publication?
yes
id
91b5a60c-0d56-4099-b3b6-58fd57636214 (old id 656686)
date added to LUP
2007-12-20 12:46:13
date last changed
2017-10-08 03:34:44
@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},
  keyword      = {EPR,electronic structure,ab initio calculations,computer chemistry,transition metals,spectroscopy},
  language     = {eng},
  number       = {12},
  pages        = {1803--1815},
  publisher    = {John Wiley & Sons},
  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},
  volume       = {8},
  year         = {2007},
}