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Quantifying the Effects of the Self-interaction Error in Density Functional Theory: When do the Delocalized States Appear? II. Iron-oxo Complexes and Closed-shell Substrate Molecules
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics.
Responsible organisation
2008 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 129, 154301- p.Article in journal (Refereed) Published
Abstract [en]

Effects of the self-interaction error (SIE) in approximate density functional theory have several times been reported and quantified for the dissociation of charged radicals, charge transfer complexes, polarizabilities, and for transition states of reactions involving main-group molecules. In the present contribution, effects of the SIE in systems composed of a catalytic transition metal complex and a closed-shell substrate molecule are investigated. For this type of system, effects of the SIE have not been reported earlier. It is found that although the best density functionals (e.g., B3LYP) are capable of accurate predictions of structure, thermodynamics, and reactivity of such systems, there are situations and systems for which the magnitude of the SIE can be large, and for which the effects can be severe for the modeling of chemical reactivity. The largest energetic effect reported here is the artificial stabilization of a catalyst-substrate complex by as much as 18 kcal/mol. Also, the disappearance of significant energy barriers for hydrogen atom transfer in certain systems are reported. In line with earlier work, it is found that the magnitude of the SIE is related to the energetics of electron transfer between the metal catalyst and the substrate molecule. It is suggested that these problems might be circumvented by the inclusion of counterions or point charges that would alter the energetics of electron transfer. It is also pointed out that the effects of SIE in the modeling of transition metal reactivity need to be investigated further.

Place, publisher, year, edition, pages
2008. Vol. 129, 154301- p.
Keyword [en]
catalysts, charge exchange, chemical exchanges, density functional theory, dissociation, free radical reactions, iron compounds, organic compounds, reaction kinetics theory, thermodynamics
National Category
Atom and Molecular Physics and Optics
Identifiers
URN: urn:nbn:se:su:diva-25474DOI: 10.1063/1.2991180ISI: 000260280600018OAI: oai:DiVA.org:su-25474DiVA: diva2:199791
Available from: 2008-09-15 Created: 2008-09-15 Last updated: 2017-12-13Bibliographically approved
In thesis
1. Biomimetic Transition Metal Catalysts: Insights from Theoretical Modeling
Open this publication in new window or tab >>Biomimetic Transition Metal Catalysts: Insights from Theoretical Modeling
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The scientific interest in the chemistry of synthetic transition metal complexes is motivated by at least two arguments:

1.These can be regarded as models of biological transition metal complexes, e.g. metalloenzymes, whose functions can be difficult to reveal in detail due to their complexity.

2.Transition metal complexes are used for catalytic purposes in the industrial synthesis of chemicals. There is a large potential for further development of this technology, which can be motivated both by economic and environmental arguments.

In the present thesis, density functional theory (a quantum mechanical method) has been applied to model reactions involving synthetic iron and copper complexes in solution. The complexity of the solvent environment is a challenging problem for theoretical investigations and a significant part of the theses has been to investigate the mechanistic effects of metal-coordinating solvent molecules, Lewis bases and counter ions. For example, it is explained why the cleavage of the O-O bond in heme-diiron-peroxides is faster in the presence of a coordinating Lewis base. Furthermore, the experimentally observed structure-activity relationship between the Fe(III)(µ-O)2Fe(IV) and (H2O)Fe(III)(µ-O)Fe(IV)O motifs is given an explanation. In addition, the present thesis presents a systematic investigation of how the self-interaction error in density functional theory (DFT) affects the modeling of transition metal catalysis.

Place, publisher, year, edition, pages
Stockholm: Fysikum, 2008. 150 p.
Keyword
Catalysis, biomimetic, copper, non-heme iron, heme iron, O2 cleavage, H-atom transfer, radical chemistry, redox chemistry, thermo chemistry, entropy calculations, quantum chemistry, spin states, density functional theory (DFT), self-interaction error (SIE).
National Category
Atom and Molecular Physics and Optics
Research subject
Chemical Physics
Identifiers
urn:nbn:se:su:diva-8197 (URN)9789171557223 (ISBN)
Public defence
2008-09-19, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00
Opponent
Supervisors
Available from: 2008-09-15 Created: 2008-09-15Bibliographically approved

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