Dissociative versus molecular chemisorption of nitric oxide on small bare cationic cobalt clusters in the gas phase

Klaassen, Joshua J.; Jacobson, D. B.

doi:10.1021/ja00211a052

Cited by 30 publications

(19 citation statements)

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“…The formation of NCO was also observed from the reduction of NO by CO on surfaces of other d metals. A similar conclusion on the presence of two isomers corresponding to an associative and dissociative attachment of NO was deduced 22 Iron is a very good catalyst. Vibrational frequencies of NO were measured using IR spectroscopy for the mononuclear 3d-to-5d transition metal nitrosyls M͑NO͒ x trapped in inert matrices, 16,17 gas-phase Au n NO + clusters 18 ͑n =1-20͒, FeNO, FeNO + , and Fe͑NO͒ 2 trapped in argon matrices, 19 and complexes NO + Fe, Co, Ni, Cu, and Zn in argon matrices.…”

Section: Introductionsupporting

confidence: 73%

Dissociative and associative attachment of NO to iron clusters

Gutsev

Mochena

Johnson

et al. 2006

The Journal of Chemical Physics

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Electronic and geometrical structures of iron clusters with associative (FeNO, Fe2NO, Fe3NO, Fe4NO, Fe5NO, and Fe6NO) and dissociative (OFeN, OFe2N, OFe3N, OFe4N, OFe5N, and OFe6N) attachments of NO, as well as the corresponding singly negatively and positively charged ions, are computed using density functional theory with generalized gradient corrections. Both types of isomers are found to be stable and no spontaneous dissociation was observed during the geometry optimizations. The ground states correspond to dissociative attachment of NO for all iron clusters Fe(n), except for Fe and Fe+. All of the OFe(n)N clusters have ferrimagnetic ground states, except for OFe2N, OFe2N-, OFe4N, and OFe4N-, which prefer the ferromagnetic coupling. In the ferrimagnetic states, the excess spin density at one iron atom couples antiferromagnetically to the excess spin densities of all other iron atoms. Relative to the high-spin Fe(n) ground state, the lowest energy ferrimagnetic state quenches the total magnetic moments of iron clusters by 7, which is to be compared with a reduction in the magnetic moment of one in the lowest energy ferromagnetic states. Dissociation of NO on the iron clusters has a pronounced impact on the energetics of reactions; the Fe(n)NO+CO-->Fe(n)N+CO2 channels are exothermic while the OFe6N+CO--> Fe6N+CO2 channels are nearly thermoneutral.

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Section: Introductionsupporting

confidence: 73%

Dissociative and associative attachment of NO to iron clusters

Gutsev

Mochena

Johnson

et al. 2006

The Journal of Chemical Physics

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“…1 in an ion trap and were reported to have a particular stability, 6 which stimulated theoretical studies on Co 2 NO 1 and Co 2 O 2 1 species. 8 For neutral dicobalt oxide molecules no structural data are, to our knowledge, yet available in the gas phase.…”

Section: Introductionmentioning

confidence: 99%

“…Gas phase studies on well-defined cobalt oxide systems, other than the diatomic molecule, are restricted to mass spectroscopic studies investigating the reactivity and kinetics for chemisorption and dissociation processes on small cationic cobalt molecules and clusters. [5][6][7] Co 2 O 2 1 cationic species have been formed in sequential reactions involving Co 2…”

Section: Introductionmentioning

confidence: 99%

Reactivity of cobalt dimer and molecular oxygen in rare gas matrices. IR spectrum, photophysics and structure of Co2O2

Danset

Manceron

2005

Phys. Chem. Chem. Phys.

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The reactivity of cobalt dimer towards molecular oxygen has been investigated in rare gas matrices. If the formation of Co2O2 from the condensation of effusive beams of Co and O2 in neon and argon matrices is observed after sample deposition, our results show that the in situ formation does not result from the reaction of ground state Co nor Co2 with molecular oxygen. One reaction channel has been evidenced through reaction of Co2 in excited states, close or above the dissociation limit. Two metastable states of Co2O2 with low-symmetry structures, stabilized by interaction with the matrix cage have also been evidenced between 1.4 and 2 eV above the ground state. Observation of Co2(16)O2, Co2(18)O2 and Co2(16)O(18)O isotopic data for five fundamental and three combination transitions enable determination of all fundamental vibrations for matrix-isolated Co2O2 in its cyclic ground state. Semi-empirical harmonic potential calculations lead to estimates of 2.435 N cm(-1) for the Co-O bond force constant, and 93 +/- 5 degrees OCoO bond angle. In comparison with the CoO diatomic molecule, this suggests a near square-planar structure with a 1.765 +/- 0.01 A CoO bond distance.

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“…Cobalt is one of the materials whose reactivity toward NO has attracted much attention because Co 3 O 4 is known to catalyze decomposition of NO 1,13 . In this respect, Klaassen and Jacobson 14,15 have observed reactions of 18 O 2 and H 2 18 O with Co n (N 16 O) + ( n = 2–4) in FT‐ICR, and have concluded that NO is molecularly chemisorbed on Co 2 + while dissociatively chemisorbed on Co 3,4 + . This finding is supported by the theoretical study of Salahub and coworkers 16 …”

Section: Introductionmentioning

confidence: 99%

Chemisorption of Nitrogen Monoxide on Size‐Selected Cobalt Cluster Ions

Hanmura

Ichihashi

Kondow

2007

Israel Journal of Chemistry

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Collisional reactions of NO with Con+ (n = 2–10) were studied by measuring the absolute cross sections for creating the product ions in a beam‐gas geometry at different collision energies and internal temperatures of Con+. The dominant reaction is chemisorption of NO on Con+ (formation of ConNO+ and Con–1NO+). As n increases, the chemisorption cross section starts to rise sharply at n = 4 and soon reaches the highest possible value, which is the Langevin cross section. The chemisorption cross section practically does not change with the internal temperature, while the branching fraction for the production of ConNO+ with respect to the sum of ConNO+ and Con–1NO+ decreases with the internal temperature in the size range of n = 6–10. A statistical model based on the RRK theory explains the dependences of the chemisorption cross section and the branching fraction on the size (n), the collision energy, and the internal temperature. The energies of the NO chemisorption derived from the dependences of the chemisorption cross section and the branching fraction on the collision energy and the internal temperature show that (1) the NO chemisorption is dissociative for n ≥ 4 and (2) more than one isomer is involved in the chemisorption of NO on Co9+.

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Dissociative versus molecular chemisorption of nitric oxide on small bare cationic cobalt clusters in the gas phase

Cited by 30 publications

References 0 publications

Dissociative and associative attachment of NO to iron clusters

Dissociative and associative attachment of NO to iron clusters

Reactivity of cobalt dimer and molecular oxygen in rare gas matrices. IR spectrum, photophysics and structure of Co2O2

Chemisorption of Nitrogen Monoxide on Size‐Selected Cobalt Cluster Ions

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