Abstract

European Journal of Mass Spectrometry
Volume 15 Issue 2, Pages 83–90 (2009)
doi: 10.1255/ejms.945

Chemistry of (and on) transition metal clusters: a Fourier transform ion cyclotron resonance study of the reaction of niobium cluster cations with nitric oxide

Daniel J. Harding,^a Thomas A.A. Oliver,^a Tiffany R. Walsh,^a,b Thomas Drewello,^a,c D. Phil Woodruff,^d Peter J. Derrick^a,e,† and Stuart R. Mackenzie^a,f,*
aDepartment of Chemistry, University of Warwick, Coventry, CV4 7AL, UK
^bCentre for Scientific Computing, University of Warwick, Coventry, CV4 7AL, UK
^cDepartment of Chemistry and Pharmacy, Physical Chemistry I, Friedrich-Alexander- Universität Erlangen-Nürnberg, Egerlandstrasse 3, 91058 Erlangen, Germany
^dDepartment of Physics, University of Warwick, Coventry, CV4 7AL, UK
^eMassey University, Institute of Fundamental Science, Private Bag 11 222, Palmerston North, New Zealand
^fUniversity Chemical Laboratories, Lensfield Road, Cambridge, CB2 1EW, UK. E-mail: srm49@cam.ac.uk; stuart.mackenzie@chem.ox.ac.uk

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 N₂ loss observed whenever multiple NO molecules are co-adsorbed. The rate constants for each process have been determined as a function of cluster size.

Keywords: FT-ICR, transition metal cluster, reaction, nitric oxide, fragmentation, decomposition

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