Accurate spin-orbit and spin-other-orbit contributions to the g-tensor for transition metal containing systems
In this paper an overview is presented of several approximations within Density Functional Theory (DFT) to calculate g-tensors in transition metal containing systems and a new accurate description of the spin-other-orbit contribution for high spin systems is suggested. Various implementations in a b...
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ftunivgent:oai:archive.ugent.be:2966885 2023-10-01T03:58:44+02:00 Accurate spin-orbit and spin-other-orbit contributions to the g-tensor for transition metal containing systems Van Yperen-De Deyne, Andy Pauwels, Ewald Van Speybroeck, Veronique Waroquier, Michel 2012 application/pdf https://biblio.ugent.be/publication/2966885 http://hdl.handle.net/1854/LU-2966885 https://doi.org/10.1039/c2cp41086a https://biblio.ugent.be/publication/2966885/file/4134111 eng eng https://biblio.ugent.be/publication/2966885 http://hdl.handle.net/1854/LU-2966885 http://dx.doi.org/10.1039/c2cp41086a https://biblio.ugent.be/publication/2966885/file/4134111 No license (in copyright) info:eu-repo/semantics/restrictedAccess PHYSICAL CHEMISTRY CHEMICAL PHYSICS ISSN: 1463-9076 Physics and Astronomy ELECTRONIC G-TENSORS DENSITY-FUNCTIONAL CALCULATIONS LASER VAPORIZATION GENERATION ORDER REGULAR APPROXIMATION EFFECTIVE NUCLEAR CHARGES CORRELATED WAVE-FUNCTIONS NMR CHEMICAL-SHIFTS 4 DEGREES-K AB-INITIO THEORETICAL CALCULATIONS journalArticle info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion 2012 ftunivgent https://doi.org/10.1039/c2cp41086a 2023-09-06T22:32:08Z In this paper an overview is presented of several approximations within Density Functional Theory (DFT) to calculate g-tensors in transition metal containing systems and a new accurate description of the spin-other-orbit contribution for high spin systems is suggested. Various implementations in a broad variety of software packages (ORCA, ADF, Gaussian, CP2K, GIPAW and BAND) are critically assessed on various aspects including (i) non-relativistic versus relativistic Hamiltonians, (ii) spin-orbit coupling contributions and (iii) the gauge. Particular attention is given to the level of accuracy that can be achieved for codes that allow g-tensor calculations under periodic boundary conditions, as these are ideally suited to efficiently describe extended condensed-phase systems containing transition metals. In periodic codes like CP2K and GIPAW, the g-tensor calculation schemes currently suffer from an incorrect treatment of the exchange spin-orbit interaction and a deficient description of the spin-other-orbit term. In this paper a protocol is proposed, making the predictions of the exchange part to the g-tensor shift more plausible. Focus is also put on the influence of the spin-other-orbit interaction which becomes of higher importance for high-spin systems. In a revisited derivation of the various terms arising from the two-electron spin-orbit and spin-other-orbit interaction (SOO), new insight has been obtained revealing amongst other issues new terms for the SOO contribution. The periodic CP2K code has been adapted in view of this new development. One of the objectives of this study is indeed a serious enhancement of the performance of periodic codes in predicting g-tensors in transition metal containing systems at the same level of accuracy as the most advanced but time consuming spin-orbit mean-field approach. The methods are first applied on rhodium carbide but afterwards extended to a broad test set of molecules containing transition metals from the fourth, fifth and sixth row of the periodic table. The ... Article in Journal/Newspaper Orca Ghent University Academic Bibliography Physical Chemistry Chemical Physics 14 30 10690 |
institution |
Open Polar |
collection |
Ghent University Academic Bibliography |
op_collection_id |
ftunivgent |
language |
English |
topic |
Physics and Astronomy ELECTRONIC G-TENSORS DENSITY-FUNCTIONAL CALCULATIONS LASER VAPORIZATION GENERATION ORDER REGULAR APPROXIMATION EFFECTIVE NUCLEAR CHARGES CORRELATED WAVE-FUNCTIONS NMR CHEMICAL-SHIFTS 4 DEGREES-K AB-INITIO THEORETICAL CALCULATIONS |
spellingShingle |
Physics and Astronomy ELECTRONIC G-TENSORS DENSITY-FUNCTIONAL CALCULATIONS LASER VAPORIZATION GENERATION ORDER REGULAR APPROXIMATION EFFECTIVE NUCLEAR CHARGES CORRELATED WAVE-FUNCTIONS NMR CHEMICAL-SHIFTS 4 DEGREES-K AB-INITIO THEORETICAL CALCULATIONS Van Yperen-De Deyne, Andy Pauwels, Ewald Van Speybroeck, Veronique Waroquier, Michel Accurate spin-orbit and spin-other-orbit contributions to the g-tensor for transition metal containing systems |
topic_facet |
Physics and Astronomy ELECTRONIC G-TENSORS DENSITY-FUNCTIONAL CALCULATIONS LASER VAPORIZATION GENERATION ORDER REGULAR APPROXIMATION EFFECTIVE NUCLEAR CHARGES CORRELATED WAVE-FUNCTIONS NMR CHEMICAL-SHIFTS 4 DEGREES-K AB-INITIO THEORETICAL CALCULATIONS |
description |
In this paper an overview is presented of several approximations within Density Functional Theory (DFT) to calculate g-tensors in transition metal containing systems and a new accurate description of the spin-other-orbit contribution for high spin systems is suggested. Various implementations in a broad variety of software packages (ORCA, ADF, Gaussian, CP2K, GIPAW and BAND) are critically assessed on various aspects including (i) non-relativistic versus relativistic Hamiltonians, (ii) spin-orbit coupling contributions and (iii) the gauge. Particular attention is given to the level of accuracy that can be achieved for codes that allow g-tensor calculations under periodic boundary conditions, as these are ideally suited to efficiently describe extended condensed-phase systems containing transition metals. In periodic codes like CP2K and GIPAW, the g-tensor calculation schemes currently suffer from an incorrect treatment of the exchange spin-orbit interaction and a deficient description of the spin-other-orbit term. In this paper a protocol is proposed, making the predictions of the exchange part to the g-tensor shift more plausible. Focus is also put on the influence of the spin-other-orbit interaction which becomes of higher importance for high-spin systems. In a revisited derivation of the various terms arising from the two-electron spin-orbit and spin-other-orbit interaction (SOO), new insight has been obtained revealing amongst other issues new terms for the SOO contribution. The periodic CP2K code has been adapted in view of this new development. One of the objectives of this study is indeed a serious enhancement of the performance of periodic codes in predicting g-tensors in transition metal containing systems at the same level of accuracy as the most advanced but time consuming spin-orbit mean-field approach. The methods are first applied on rhodium carbide but afterwards extended to a broad test set of molecules containing transition metals from the fourth, fifth and sixth row of the periodic table. The ... |
format |
Article in Journal/Newspaper |
author |
Van Yperen-De Deyne, Andy Pauwels, Ewald Van Speybroeck, Veronique Waroquier, Michel |
author_facet |
Van Yperen-De Deyne, Andy Pauwels, Ewald Van Speybroeck, Veronique Waroquier, Michel |
author_sort |
Van Yperen-De Deyne, Andy |
title |
Accurate spin-orbit and spin-other-orbit contributions to the g-tensor for transition metal containing systems |
title_short |
Accurate spin-orbit and spin-other-orbit contributions to the g-tensor for transition metal containing systems |
title_full |
Accurate spin-orbit and spin-other-orbit contributions to the g-tensor for transition metal containing systems |
title_fullStr |
Accurate spin-orbit and spin-other-orbit contributions to the g-tensor for transition metal containing systems |
title_full_unstemmed |
Accurate spin-orbit and spin-other-orbit contributions to the g-tensor for transition metal containing systems |
title_sort |
accurate spin-orbit and spin-other-orbit contributions to the g-tensor for transition metal containing systems |
publishDate |
2012 |
url |
https://biblio.ugent.be/publication/2966885 http://hdl.handle.net/1854/LU-2966885 https://doi.org/10.1039/c2cp41086a https://biblio.ugent.be/publication/2966885/file/4134111 |
genre |
Orca |
genre_facet |
Orca |
op_source |
PHYSICAL CHEMISTRY CHEMICAL PHYSICS ISSN: 1463-9076 |
op_relation |
https://biblio.ugent.be/publication/2966885 http://hdl.handle.net/1854/LU-2966885 http://dx.doi.org/10.1039/c2cp41086a https://biblio.ugent.be/publication/2966885/file/4134111 |
op_rights |
No license (in copyright) info:eu-repo/semantics/restrictedAccess |
op_doi |
https://doi.org/10.1039/c2cp41086a |
container_title |
Physical Chemistry Chemical Physics |
container_volume |
14 |
container_issue |
30 |
container_start_page |
10690 |
_version_ |
1778531859062325248 |