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, Thomas A A Oliver, Tiffany R Walsh, Thomas Drewello, D Phil Woodruff, Peter J Derrick, Stuart R Mackenzie

Research output: Contribution to journalArticle (Academic Journal)

Abstract

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.

Original languageEnglish
Pages (from-to)83-90
Number of pages8
JournalEuropean Journal of Mass Spectrometry
Volume15
Issue number2
DOIs
Publication statusPublished - 2009

Keywords

  • Adsorption
  • Cations
  • Fourier Analysis
  • Kinetics
  • Mass Spectrometry
  • Molecular Structure
  • Niobium
  • Nitric Oxide
  • Oxides
  • Quantum Theory

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