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Modelling the visible absorption spectra of copper(II) acetylacetonate by density functional theory
Univ Fed Minas Gerais, Dept Quim.
Univ Fed Minas Gerais, Dept Quim.
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
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2010 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 492, no 1-3, 14-18 p.Article in journal (Refereed) Published
Abstract [en]

Spin restricted open-shell Density Functional Theory calculations have been carried out by means of linear response theory to investigate the visible absorption spectrum of copper(II) acetylacetonate complex, Cu(acac)(2). The 3d -> 3d transition energies and the influence of molecular structure and non-coordinating solvent on the spectra have been investigated. The obtained four 3d -> 3d transition energies accord well with the experimental data in the crystal phase. The presented results indicate that the experimentally observed four band structure of Cu(acac)(2) is of molecular nature, and not caused by factor-group splitting in the crystal environment as previously suggested.

Place, publisher, year, edition, pages
2010. Vol. 492, no 1-3, 14-18 p.
Keyword [en]
ELECTRONIC ABSORPTION; RESONANCE RAMAN; BASIS-SET; COMPLEXES; PROTEIN; EXCHANGE; PLANAR
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-8425DOI: 10.1016/j.cplett.2010.04.022ISI: 000277717300003Scopus ID: 2-s2.0-77953291481OAI: oai:DiVA.org:kth-8425DiVA: diva2:13740
Note
QC 20100714. Uppdaterad från manuskript till artikel (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
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Note
QC 20100714Available from: 2008-05-12 Created: 2008-05-12 Last updated: 2010-07-14Bibliographically approved

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Vahtras, OlavÅgren, Hans

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