TY - JOUR
T1 - Chemistry of (and on) transition metal clusters
T2 - a Fourier transform ion cyclotron resonance study of the reaction of niobium cluster cations with nitric oxide
AU - Harding, Daniel J
AU - Oliver, Thomas A A
AU - Walsh, Tiffany R
AU - Drewello, Thomas
AU - Woodruff, D Phil
AU - Derrick, Peter J
AU - Mackenzie, Stuart R
PY - 2009
Y1 - 2009
N2 - 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.
AB - 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.
KW - Adsorption
KW - Cations
KW - Fourier Analysis
KW - Kinetics
KW - Mass Spectrometry
KW - Molecular Structure
KW - Niobium
KW - Nitric Oxide
KW - Oxides
KW - Quantum Theory
U2 - 10.1255/ejms.945
DO - 10.1255/ejms.945
M3 - Article
VL - 15
SP - 83
EP - 90
JO - European Journal of Mass Spectrometry
JF - European Journal of Mass Spectrometry
SN - 1356-1049
IS - 2
ER -