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Density functional theory study of indirect nuclear spin-spin coupling constants with spin-orbit corrections
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0003-2729-0290
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0002-9123-8174
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0002-1763-9383
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2005 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 123, no 1, 014101-1-014101-10 p.Article in journal (Refereed) Published
Abstract [en]

This work outlines the calculation of indirect nuclear spin-spin coupling constants with spin-orbit corrections using density functional response theory. The nonrelativistic indirect nuclear spin-spin couplings are evaluated using the linear response method, whereas the relativistic spin-orbit corrections are computed using quadratic response theory. The formalism is applied to the homologous systems H2X (X= O, S, Se, Te) and XH4 (X= C, Si, Ge, Sn, Pb) to calculate the indirect nuclear spin-spin coupling constants between the protons. The results confirm that spin-orbit corrections are important for compounds of the H2X series, for which the electronic structure allows for an efficient coupling between the nuclei mediated by the spin-orbit interaction, whereas in the case of the XH4 series the opposite situation is encountered and the spin-orbit corrections are negligible for all compounds of this series. In addition we analyze the performance of the density functional theory in the calculations of nonrelativistic indirect nuclear spin-spin coupling constants.

Place, publisher, year, edition, pages
2005. Vol. 123, no 1, 014101-1-014101-10 p.
Keyword [en]
Correlation methods; Electronic structure; Lead compounds; Molecular structure; Nuclear magnetic resonance spectroscopy; Tin compounds; Density functional theory (DFT); Geometrical structures; Molecular systems; Spin-spin coupling constants; Electron energy levels
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-7067DOI: 10.1063/1.1947190ISI: 000230493600002Scopus ID: 2-s2.0-22844452433OAI: oai:DiVA.org:kth-7067DiVA: diva2:11969
Note
QC 20100811Available from: 2007-05-11 Created: 2007-05-11 Last updated: 2010-08-11Bibliographically approved
In thesis
1. Density Functional Response Theory with Applications to Electron and Nuclear Magnetic Resonance
Open this publication in new window or tab >>Density Functional Response Theory with Applications to Electron and Nuclear Magnetic Resonance
2007 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis presents quantum chemical calculations, applications of the response function formalism recently implemented within the framework of density functional theory by our research group. The purpose of the calculations is to assess the performance of this perturbative approach to determining heavy atom effects on magnetic resonance parameters. Relativistic corrections can be generated by spin-orbit interactions or by scalar relativistic effects due to high velocity electrons in the atomic core region of heavy atoms. In this work, the evaluation of nuclear magnetic resonance parameters is considered, the nuclear shielding tensor and the indirect nuclear spin-spin coupling tensor. For series of homologous compounds, it is found that both types of corrections to these parameters are increasing in size upon substitution of a constituent atom by a heavier element, but that their relative importance is system dependent. The obtained results are compatible with the ones provided by electron correlated ab initio methods, and a qualitative agreement with experimentally determined parameters is overall achieved. The methodology presented in this thesis aims to be a practical approach which can be applied in the study of molecular properties of large systems.

This thesis also addresses the calculation of hyperfine coupling constants, and evaluates a novel approach to the treatment of spin-polarization in spin restricted calculations without the spin contamination associated with spin unrestricted calculations

Place, publisher, year, edition, pages
Stockholm: KTH, 2007. v, 51 p.
Keyword
biochemistry, molecular physics, computer science
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-4367 (URN)978-91-7178-675-3 (ISBN)
Public defence
2007-05-25, FA32, AlbaNova, Roslagstullsbacken, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100811Available from: 2007-05-11 Created: 2007-05-11 Last updated: 2010-08-11Bibliographically approved
2. Theoretical calculations of heavy atom effects in magnetic resonance spectroscopy
Open this publication in new window or tab >>Theoretical calculations of heavy atom effects in magnetic resonance spectroscopy
2006 (English)Licentiate thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis presents quantum chemical calculations, applications of the response function formalism recently implemented within the framework of density functional theory (DFT) by our research group. The purpose of the calculations is to assess the performance of this perturbative approach to determining heavy atom effects on magnetic resonance parameters. Relativistic corrections can be generated by spin-orbit interactions or by scalar relativistic effects due to high velocity electrons in the atomic core region of heavy atoms. In this work, the evaluation of nuclear magnetic resonance (NMR) parameters is considered, the nuclear shielding tensor and the indirect nuclear spin-spin coupling tensor. For series of homologous compounds, it is found that both types of corrections to these parameters are increasing in size upon substitution of a constituent atom by a heavier element, but that their relative importance is system dependent. The obtained results are compatible with the ones provided by electron correlated ab initio methods, and a qualitative agreement with experimentally determined parameters is overall achieved. The methodology presented in this thesis aims to be a practical approach which can be applied in the study of molecular properties of large systems.

This thesis also addresses the calculation of hyperfine coupling constants, and evaluates a novel approach to the treatment of spin-polarization in spin restricted calculations without the spin contamination associated with spin unrestricted calculations.

Place, publisher, year, edition, pages
Stockholm: Bioteknologi, 2006. v, 28 p.
Keyword
nuclear spin-spin coupling tensor, nuclear shielding tensor, heavy atom effect, hyperfine coupling tensor, restricted-unrestricted approach
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-3971 (URN)91-7178-351-2 (ISBN)
Presentation
2006-05-30, Sal FB53, AlbaNova, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20101122Available from: 2006-05-17 Created: 2006-05-17 Last updated: 2010-11-22Bibliographically approved

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Vahtras, OlavÅgren, Hans

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