Journal of Chemical Physics, Vol.116, No.3, 936-945, 2002
Guided ion beam studies of the reactions of V-n(+) (n=2-13) with D-2: Cluster-deuteride bond energies as a chemical probe of cluster electronic structure
The kinetic energy dependencies of the reactions of V-n(+) (n=2-13) with D-2 are studied in a guided ion beam tandem mass spectrometer. Products observed are VnD+ for all clusters and VnD2+ for n=4-13. All reactions are observed to exhibit thresholds, except for formation of VnD2+ for n=4,5,7,9,11-13. The enhanced reactivity of the odd-sized clusters towards D-2 chemisorption is nicely correlated with the D-0(V-n(+)-V) bond energies. The odd-number clusters are less stable and more reactive, suggesting that they are open shell, whereas the even-number clusters, which are more stable and less reactive, appear to be closed shell. Threshold analyses of the endothermic reactions lead to V-n(+)-D binding energies (n=1-13), which reach values comparable to the bulk phase for larger clusters. The V-n(+)-D bond energies show odd-even oscillations anticorrelated with D-0(V-n(+)-V) for n <5, but roughly parallel with D-0(V-n(+)-V) for n >5. Magnitude differences in the two series of bond energies suggest that the metal-metal bonding has appreciable 3d-3d contributions. The variation in the V-n(+)-D bond energies with cluster size is explained using promotion energy arguments.