Oxygen-transfer reactions between 3d transition metals and N2O and NO2

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Abstract

Density functional calculations have been performed to describe reactions of ground-state 3d transition metal atoms (Sc-Ni) with N2O and NO2 molecules. From the analysis of the calculated reaction surfaces, a general reaction mechanism evolved. The reactions are initiated by electron transfer from metal to the oxidant molecule, which weakens the N-O bond and facilitates an O-(2P) abstraction. 4s-3d hybridization taking place in the metal electronic structure plays an essential role in the net 4sβ electron transfer from the metal atom to the nitrogen-oxide molecule. These key steps contribute to connect the reactant and product channels on a single potential energy surface. The calculations revealed that reaction with NO2 yields stable oxo-nitrosyl insertion products, and their equilibrium structural properties can be understood by inspecting the 4π* metal-oxide orbital occupancies. Correlation is obtained between the metal 3d ionization energies and the reaction rates as well as activation energies. This correlation provides additional support for the reaction mechanism called electron-transfer-assisted oxygen abstraction. This novel mechanism exhibits the basic features of the simple electron transfer and direct abstraction kinetic models and sheds new light on the so-called resonance interaction model as well.

Original languageEnglish
Pages (from-to)4058-4067
Number of pages10
JournalJournal of the American Chemical Society
Volume124
Issue number15
DOIs
Publication statusPublished - Apr 17 2002

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Transition metals
Metals
Oxygen
Electrons
Molecules
Atoms
Potential energy surfaces
Ionization potential
Nitrogen oxides
Surface reactions
Oxidants
Oxides
Ground state
Reaction rates
Electronic structure
Density functional theory
Structural properties
Nitric Oxide
Activation energy
Kinetics

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Oxygen-transfer reactions between 3d transition metals and N2O and NO2. / Stirling, A.

In: Journal of the American Chemical Society, Vol. 124, No. 15, 17.04.2002, p. 4058-4067.

Research output: Contribution to journalArticle

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abstract = "Density functional calculations have been performed to describe reactions of ground-state 3d transition metal atoms (Sc-Ni) with N2O and NO2 molecules. From the analysis of the calculated reaction surfaces, a general reaction mechanism evolved. The reactions are initiated by electron transfer from metal to the oxidant molecule, which weakens the N-O bond and facilitates an O-(2P) abstraction. 4s-3d hybridization taking place in the metal electronic structure plays an essential role in the net 4sβ electron transfer from the metal atom to the nitrogen-oxide molecule. These key steps contribute to connect the reactant and product channels on a single potential energy surface. The calculations revealed that reaction with NO2 yields stable oxo-nitrosyl insertion products, and their equilibrium structural properties can be understood by inspecting the 4π* metal-oxide orbital occupancies. Correlation is obtained between the metal 3d ionization energies and the reaction rates as well as activation energies. This correlation provides additional support for the reaction mechanism called electron-transfer-assisted oxygen abstraction. This novel mechanism exhibits the basic features of the simple electron transfer and direct abstraction kinetic models and sheds new light on the so-called resonance interaction model as well.",
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AB - Density functional calculations have been performed to describe reactions of ground-state 3d transition metal atoms (Sc-Ni) with N2O and NO2 molecules. From the analysis of the calculated reaction surfaces, a general reaction mechanism evolved. The reactions are initiated by electron transfer from metal to the oxidant molecule, which weakens the N-O bond and facilitates an O-(2P) abstraction. 4s-3d hybridization taking place in the metal electronic structure plays an essential role in the net 4sβ electron transfer from the metal atom to the nitrogen-oxide molecule. These key steps contribute to connect the reactant and product channels on a single potential energy surface. The calculations revealed that reaction with NO2 yields stable oxo-nitrosyl insertion products, and their equilibrium structural properties can be understood by inspecting the 4π* metal-oxide orbital occupancies. Correlation is obtained between the metal 3d ionization energies and the reaction rates as well as activation energies. This correlation provides additional support for the reaction mechanism called electron-transfer-assisted oxygen abstraction. This novel mechanism exhibits the basic features of the simple electron transfer and direct abstraction kinetic models and sheds new light on the so-called resonance interaction model as well.

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