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  Theoretical Study on the Mechanism of Reaction of Ground-State Fe Atoms with Carbon Dioxide

Pantazis, D. A., Tsipis, A. C., & Tsipis, C. A. (2004). Theoretical Study on the Mechanism of Reaction of Ground-State Fe Atoms with Carbon Dioxide. Collection of Czechoslovak Chemical Communications, 69(1), 13-33. doi:10.1135/cccc20040013.

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 Creators:
Pantazis, Dimitrios A.1, Author              
Tsipis, Athanassios C.1, Author
Tsipis, Constantinos A.1, Author
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1Laboratory of Applied Quantum Chemistry, Faculty of Chemistry, Aristotle University of Thessaloniki, 540 06 Thessaloniki, Greece, ou_persistent22              

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Free keywords: DFT; FeCO2 complexes; CO2-to-CO reduction; Reaction mechanism; Electronic structure; Ab initio calculations; Iron
 Abstract: Density functional calculations at the B3LYP level of theory, using the 6-31G(d) and 6-311+G(3df) basis sets, provide a satisfactory description of the geometric and energetic reaction profile of the Fe + CO2 → FeO + CO reaction. The reaction is predicted to be endothermic by 23.24 kcal/mol at the B3LYP/6-311+G(3df)//B3LYP/6-31G(d) level of theory and to proceed by formation of either a Fe(η2-OCO) or a Fe(η3-OCO) intermediate. The Fe(η2-OCO) intermediate in the 5A' ground state is weakly bound with respect to Fe(5D) and CO2 dissociation products by 0.78 (2.88) kcal/mol at the B3LYP/6-31G(d) (B3LYP/6-311+ G(3df)//B3LYP/6-31G(d)) levels of theory. In contrast, the Fe(η3-OCO) intermediate in the 5A1 ground state is unbound with respect to Fe(5D) and CO2 dissociation products by 8.27 (11.15) kcal/mol at the same levels of theory. However, both intermediates are strongly bound relative to the separated Fe+(6D) and [CO2]- anion; the computed bond dissociation energies for the Fe(η2-OCO) and Fe(η3-OCO) intermediates are 207.33 and 198.28 kcal/mol in terms of ∆E0 at the B3LYP/6-31G(d), respectively. In the Fe(η2-OCO) and Fe(η3-OCO) intermediates, an intramolecular insertion reaction of the Fe atom to O-C bond takes place yielding the isomeric OFe(η1-CO) and OFe(η1-OC) products, respectively, with a relatively low activation barrier of 25.24 (21.69) and 26.36 (23.38) kcal/mol at the B3LYP/6-31G(d) (B3LYP/6-311+G(3df)//B3LYP/6-31G(d)) levels of theory, respectively. The calculated structures, relative stability and bonding properties of all stationary points are discussed with respect to computed electronic and spectroscopic properties, such as charge density distribution and harmonic vibrational frequencies.

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Language(s): eng - English
 Dates: 2004-01
 Publication Status: Published in print
 Pages: 21
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1135/cccc20040013
 Degree: -

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Title: Collection of Czechoslovak Chemical Communications
  Other : Collect. Czech. Chem. Commun.
Source Genre: Journal
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Publ. Info: Prague : Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic [etc.]
Pages: - Volume / Issue: 69 (1) Sequence Number: - Start / End Page: 13 - 33 Identifier: ISSN: 0010-0765
CoNE: https://pure.mpg.de/cone/journals/resource/954925391300