Chemistry of (and on) transition metal clusters: a Fourier transform ion cyclotron resonance study of the reaction of niobium cluster cations with nitric oxide.
The reactions of niobium cluster cations, Nb(+)(n) (n = 2-19), with nitric oxide have been investigated using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR). The overall reaction rate constants are found to be in reasonable agreement with collision rates calculated using the surface charge capture model. The dominant reaction for small clusters (n <9) involves reaction-induced fragmentation resulting in the loss of either NbO or NbN. By contrast, the main reaction observed for the larger clusters (n> 11) is sequential NO chemisorption. Clusters n = 9, 10 exhibit both extremes of behaviour and are the only clusters upon which there is evidence of NO decomposition with N(2) loss observed whenever multiple NO molecules are co-adsorbed. The rate constants for each process have been determined as a function of cluster size.
Departm ent of Chemistry, University of Warwick, Coventry, CV4 7AL, UK.
Daniel J
DJ
Harding
Thomas A A
TA
Oliver
Tiffany R
TR
Walsh
Thomas
T
Drewello
D Phil
DP
Woodruff
Peter J
PJ
Derrick
Stuart R
SR
Mackenzie
D000327:Adsorption; D002412:Cations / Q000737:chemistry; D005583:Fourier Analysis; D007700:Kinetics; D013058:Mass Spectrometry / Q000379:methods*; D015394:Molecular Structure; D009556:Niobium / Q000737:chemistry*; D009569:Nitric Oxide / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry; D011789:Quantum Theory
D002412:Cations; D010087:Oxides; D009556:Niobium; D009569:Nitric Oxide