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
Conformations, structural transitions and visible near-infrared absorption spectra of four-, five- and six-coordinated Cu(II) aqua complexes
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).ORCID iD: 0000-0003-0185-5724
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).ORCID iD: 0000-0003-2729-0290
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).ORCID iD: 0000-0001-8748-3890
Show others and affiliations
2009 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 11, no 3, 508-519 p.Article in journal (Refereed) Published
Abstract [en]

We have performed Car-Parrinello molecular dynamics simulations at ambient conditions for four-, five- and six-coordinated Cu(II) aqua complexes. The molecular geometry has been investigated in terms of Cu-O, Cu-H bond lengths and O-Cu-O bond angles and compared with earlier experimental measurement results and theoretical calculations. We find that the average Cu-O and Cu-H bond lengths increase with increasing coordination number. We have also observed relatively faster structural transition in the case of five- coordinated complex between trigonal bipyramidal and square pyramidal geometry. This result deviates from the findings of the earlier report (A. Pasquarello et al., Science, 2001, 291, 856) on copper( II) in aqueous solution and we attribute these differences to the neglect of solvent environment in our calculations. The averaged absorption spectra for the copper( II) aqua complexes have been computed using spin-restricted density functional linear response formalism taking 100 snap shots from a trajectory of 0.48 ps. We find that the calculated spectra are significantly different, showing clear features that distinguish each coordination model. Comparison with the experimentally reported absorption spectra is made wherever it is possible and the results obtained favor the distorted fivefold-coordination arrangement for the molecular structure of the Cu(II) ion in aqueous solution.

Place, publisher, year, edition, pages
2009. Vol. 11, no 3, 508-519 p.
Keyword [en]
MOLECULAR-DYNAMICS SIMULATION; DENSITY-FUNCTIONAL THEORY; GAUSSIAN-BASIS SETS; COPPER CENTERS; SPECTROSCOPIC PROPERTIES; ELECTRONIC-STRUCTURE; HYDRATED IONS; ATOMS LI; CU2+; SOLVATION
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-8424DOI: 10.1039/b806423gISI: 000262007000008Scopus ID: 2-s2.0-58149174187OAI: oai:DiVA.org:kth-8424DiVA: diva2:13739
Note

QC 20100714. Uppdaterad från submitted till published (20100714).

Available from: 2008-05-12 Created: 2008-05-12 Last updated: 2013-03-13Bibliographically 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

Natarajan Arul, MuruganHugosson, Håkan WilhelmVahtras, OlavÅgren, Hans

Search in DiVA

By author/editor
de Almeida, Katia JúliaNatarajan Arul, MuruganRinkevicius, ZilvinasHugosson, Håkan WilhelmVahtras, OlavÅgren, HansCesar, Amary
By organisation
Theoretical Chemistry (closed 20110512)
In the same journal
Physical Chemistry, Chemical Physics - PCCP
Chemical Sciences

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 96 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