Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Degenerate perturbation theory for electronic g tensors: leading-order relativistic effects
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0003-2729-0290
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0002-9123-8174
Show others and affiliations
2008 (English)In: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 4, no 11, 1810-1828 p.Article in journal (Refereed) Published
Abstract [en]

A new approach for the evaluation of the leading-order relativistic corrections to the electronic g tensors of molecules with a doublet ground state is presented. The methodology is based on degenerate perturbation theory and includes all relevant contributions to the g tensor shift up to order theta(alpha(4)) originating from the one-electron part of the Breit-Pauli Hamiltonian-that is, it allows for the treatment of scalar relativistic, spin-orbit, and mixed corrections to the spin and orbital Zeeman effects. This approach has been implemented in the framework of spin-restricted density functional theory and is in the present paper, as a first illustration of the theory, applied to study relativistic effects on electronic g tensors of dihalogen anion radicals X-2(-) (X = F, Cl, Br, I). The results indicate that the spin-orbit interaction is responsible for the large parallel component of the g tensor shift of Br-2(-) and I-2(-), and furthermore that both the leading-order scalar relativistic and spin-orbit corrections are of minor importance for the perpendicular component of the g tensor in these molecules since they effectively cancel each other. In addition to investigating the g tensors of dihalogen anion radicals, we also critically examine the importance of various relativistic corrections to the electronic g tensor of linear molecules with Sigma-type ground states and present a two-state model suitable for an approximate estimation of the g tensor in such molecules.

Place, publisher, year, edition, pages
2008. Vol. 4, no 11, 1810-1828 p.
Keyword [en]
DENSITY-FUNCTIONAL CALCULATIONS; TRANSITION-METAL-COMPLEXES; PARAMAGNETIC MOLYBDENUM COMPLEXES; SPIN-ORBIT OPERATORS; RESONANCE PARAMETERS; MAGNETIC-PROPERTIES; RESPONSE THEORY; HARTREE-FOCK; G-VALUES; EPR
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-8428DOI: 10.1021/ct800053fISI: 000260851300002Scopus ID: 2-s2.0-58149214184OAI: oai:DiVA.org:kth-8428DiVA: diva2:13743
Note
QC 20100714. Uppdaterad från submitted till published (20100714).Available from: 2008-05-12 Created: 2008-05-12 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Optical and Magnetic Properties of Copper(II) Compounds
Open this publication in new window or tab >>Optical and Magnetic Properties of Copper(II) Compounds
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis encloses quantum chemical calculations and applications of a response function formalism recently implemented within the framework of density functional theory. The optical and magnetic properties of copper(II) molecular systems are the main goal of this work. In this work, the visible and near-infrared electronic transitions, which have shown a key role in studies on electronic structure and structure-function relationships of copper compounds, were investigated in order to explore the correlation of the positions and intensities of these transitions with the geometrical structures and their molecular distortions. The evaluation of solvent effects on the absorption spectra were successfully achieved, providing accurate and inedit computational insight of these effects for copper(II) complexes. Electron Paramagnetic Resonance (EPR) parameters, that is, the electronic g tensor and the hyperfine coupling constants, are powerful spectroscopic properties for investigating paramagnetic systems and were thoroughly analysed in this work in different molecular systems. Relativistic corrections generated by spin-orbit interactions or by scalar relativistic effects were taken into account in all calculations. In addition, we have designed a methodology for accurate evaluation of the electronic g tensors and hyperfine coupling tensors as well as for evaluation of solvent effects on these properties. It is found that this methodology is able to provide reliable and accurate results for EPR parameters of copper(II) molecular systems. The spin polarization effects on EPR parameters of square planar copper(II) complexes were also considered, showing that these effects give rise to significant contributions to the hyperfine coupling tensor, whereas the electronic g tensor of these complexes are only marginally affected by these effects. The evaluation of the leading-order relativistic corrections to the electronic g tensors of molecules with a doublet ground state has been also taken into account in this work. As a first application of the theory, the electronic g tensors of dihalogen anion radicals X$_2^-$ (X=F,~Cl,~Br,~I) have been investigated and the obtained results indicate that the spin--orbit interaction is responsible for the parallel component of the g tensor shift, while both the leading-order scalar relativistic and spin--orbit corrections are of minor importance for the perpendicular component of the g tensor in these molecules

since they effectively cancel each other. Overall, both optical and magnetic results show quantitative agreements with experiments, indicating that the methodologies employed form a practical way in study of copper(II) molecular systems including those of biological importance.

Place, publisher, year, edition, pages
Stockholm: KTH, 2008. vi, 53 p.
National Category
Industrial Biotechnology
Identifiers
urn:nbn:se:kth:diva-4743 (URN)978-91-7415-014-8 (ISBN)
Public defence
2008-05-30, FA32, AlbaNova, Roslagstullsbacken, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100714Available from: 2008-05-12 Created: 2008-05-12 Last updated: 2010-07-14Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Authority records BETA

Vahtras, OlavÅgren, Hans

Search in DiVA

By author/editor
Rinkevicius, Zilvinasde Almeida, Katia JúliaOprea, Corneliu I.Vahtras, OlavÅgren, Hans
By organisation
Theoretical Chemistry
In the same journal
Journal of Chemical Theory and Computation
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 55 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf