Correlated four-component EPR g-tensors for doublet molecules

M.S. Vad, M.N. Pedersen, A. Nørager, Hans Jørgen Aagaard Jensen

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

The first correlated ab initio four-component calculations of electron paramagnetic resonance (EPR) g-tensors for doublet radicals are reported. We have implemented a first-order degenerate perturbation theory approach based on the four-component Dirac-Coulomb Hamiltonian and fully relativistic configuration interaction wave functions in the DIRAC program package. We find that the correlation effects on the g-tensors can be sufficiently well described with manageable basis sets of triple-zeta quality and manageable configuration spaces. The new fully relativistic EPR module in DIRAC should be useful for benchmarking density functional theory approaches, however, with future optimization of the code we believe it will also be useful for applications.
OriginalsprogEngelsk
Artikelnummer214106
TidsskriftJournal of Chemical Physics
Vol/bind138
Udgave nummer21
ISSN0021-9606
DOI
StatusUdgivet - 2013

Fingeraftryk

Tensors
Paramagnetic resonance
electron paramagnetic resonance
tensors
Hamiltonians
Molecules
Benchmarking
Wave functions
configuration interaction
Density functional theory
molecules
perturbation theory
modules
wave functions
density functional theory
optimization
configurations

Citer dette

@article{ae3095795cc3486ea31af12aa1a893d2,
title = "Correlated four-component EPR g-tensors for doublet molecules",
abstract = "The first correlated ab initio four-component calculations of electron paramagnetic resonance (EPR) g-tensors for doublet radicals are reported. We have implemented a first-order degenerate perturbation theory approach based on the four-component Dirac-Coulomb Hamiltonian and fully relativistic configuration interaction wave functions in the DIRAC program package. We find that the correlation effects on the g-tensors can be sufficiently well described with manageable basis sets of triple-zeta quality and manageable configuration spaces. The new fully relativistic EPR module in DIRAC should be useful for benchmarking density functional theory approaches, however, with future optimization of the code we believe it will also be useful for applications.",
author = "M.S. Vad and M.N. Pedersen and A. N{\o}rager and Jensen, {Hans J{\o}rgen Aagaard}",
year = "2013",
doi = "10.1063/1.4804352",
language = "English",
volume = "138",
journal = "The Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics",
number = "21",

}

Correlated four-component EPR g-tensors for doublet molecules. / Vad, M.S.; Pedersen, M.N.; Nørager, A.; Jensen, Hans Jørgen Aagaard.

I: Journal of Chemical Physics, Bind 138, Nr. 21, 214106, 2013.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Correlated four-component EPR g-tensors for doublet molecules

AU - Vad, M.S.

AU - Pedersen, M.N.

AU - Nørager, A.

AU - Jensen, Hans Jørgen Aagaard

PY - 2013

Y1 - 2013

N2 - The first correlated ab initio four-component calculations of electron paramagnetic resonance (EPR) g-tensors for doublet radicals are reported. We have implemented a first-order degenerate perturbation theory approach based on the four-component Dirac-Coulomb Hamiltonian and fully relativistic configuration interaction wave functions in the DIRAC program package. We find that the correlation effects on the g-tensors can be sufficiently well described with manageable basis sets of triple-zeta quality and manageable configuration spaces. The new fully relativistic EPR module in DIRAC should be useful for benchmarking density functional theory approaches, however, with future optimization of the code we believe it will also be useful for applications.

AB - The first correlated ab initio four-component calculations of electron paramagnetic resonance (EPR) g-tensors for doublet radicals are reported. We have implemented a first-order degenerate perturbation theory approach based on the four-component Dirac-Coulomb Hamiltonian and fully relativistic configuration interaction wave functions in the DIRAC program package. We find that the correlation effects on the g-tensors can be sufficiently well described with manageable basis sets of triple-zeta quality and manageable configuration spaces. The new fully relativistic EPR module in DIRAC should be useful for benchmarking density functional theory approaches, however, with future optimization of the code we believe it will also be useful for applications.

UR - http://www.scopus.com/inward/record.url?scp=84879172813&partnerID=8YFLogxK

U2 - 10.1063/1.4804352

DO - 10.1063/1.4804352

M3 - Journal article

VL - 138

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 21

M1 - 214106

ER -