Calculation of electronic g-tensors using coupled cluster theory

Jürgen Gauss, M. Kállay, Frank Neese

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

A scheme for the calculation of the electronic g-tensor at the coupled cluster (CC) level is presented. The reported implementation employs an effective one-electron spin-orbit operator, allows the inclusion of arbitrary excitations in the cluster operator, and offers various options concerning the treatment of orbital relaxation and choice of reference determinants. In addition, the use of gauge-including atomic orbitais (GIAOs) is possible to overcome the gauge origin problem. Benchmark calculations for the NH ( 3Σ-) radical reveal the importance of electron correlation effects for the accurate prediction of the g-shift as well as the slow basis set convergence of such calculations, which is only marginally improved by using GIAOs. CC singles and doubles results for the g-tensor are furthermore used to validate various functionals often used in density functional theory calculations. At least for radicals containing only light elements, the B3LYP hybrid functional appears to be the best among the four functionals tested in the present work.

Original languageEnglish
Pages (from-to)11541-11549
Number of pages9
JournalJournal of Physical Chemistry A
Volume113
Issue number43
DOIs
Publication statusPublished - Oct 29 2009

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Tensors
tensors
Gages
electronics
functionals
operators
Electron correlations
light elements
determinants
electron spin
Density functional theory
Orbits
inclusions
density functional theory
orbits
orbitals
Electrons
shift
predictions
excitation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Calculation of electronic g-tensors using coupled cluster theory. / Gauss, Jürgen; Kállay, M.; Neese, Frank.

In: Journal of Physical Chemistry A, Vol. 113, No. 43, 29.10.2009, p. 11541-11549.

Research output: Contribution to journalArticle

Gauss, Jürgen ; Kállay, M. ; Neese, Frank. / Calculation of electronic g-tensors using coupled cluster theory. In: Journal of Physical Chemistry A. 2009 ; Vol. 113, No. 43. pp. 11541-11549.
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