In previous work, guided ion beam tandem mass spectrometry has been used to study the reactions of the cluster cations of several transition metals (V, Cr, Fe and Ni) with D2, O2, CO2 and CD4. By examining the kinetic energy dependence of these reactions and interpreting thresholds observed for various reactions, bond energies for D, O, C, CD, CD2 and CD3 can be obtained. The results of these studies are reviewed with an emphasis on the relationship between the thermochemistry obtained from this work with that for adsorbates on bulk-phase metal surfaces. It is found that in cases where quantitative comparison can be made, for example D and O atoms, modest sized clusters bind these species to approximately the same extent as the bulk-phase surface of the same metal. As there is little information available for the molecular fragments investigated here, the cluster bond energies provide some of the first experimental values for such adsorbates on surfaces.
SomorjaiG., Chemistry in Two Dimensions: Surfaces.Cornell University Press, Ithaca, NY, USA (1981).
2.
OverH.KimY.D.SeitsonenA.P.WendtS.LundgrenE.SchmidM.VargaP.MorganteA. and ErtlG., Science287, 1474 (2000).
3.
LianL.SuC.X. and ArmentroutP.B., J. Chem. Phys.97, 4084 (1992).
4.
SuC.X.HalesD.A. and ArmentroutP.B., J. Chem. Phys.99, 6613 (1993).
5.
SuC.X.HalesD.A. and ArmentroutP.B., Chem. Phys. Lett.201, 199 (1993).
6.
SuC.X. and ArmentroutP.B., J. Chem. Phys.99, 6506 (1993).
7.
ErvinK.LohS.K.AristovN. and ArmentroutP.B., J. Phys. Chem.87, 3593 (1983).
8.
ArmentroutP.B., in Laser Applications in Chemistry and Biophysics, Ed by El-SayedM.Proc. SPIE, 620, 38 (1986).
9.
LohS.K.HalesD.A.LianL. and ArmentroutP.B., J. Chem. Phys.90, 5466 (1989).
10.
LohS.K.LianL.HalesD.A. and ArmentroutP.B., J. Phys. Chem.92, 4009 (1988).
11.
LianL.SuC.X. and ArmentroutP.B., J. Chem. Phys.97, 4072 (1992).
12.
HalesD.A. and ArmentroutP.B., J. Cluster Science1, 127 (1990).
13.
HalesD.A.SuC.X. and ArmentroutP.B., J. Chem. Phys.100, 1049 (1994).
14.
LianL.SuC.X. and ArmentroutP.B., Chem. Phys. Lett.180, 168 (1991).
15.
LianL.SuC.X. and ArmentroutP.B., J. Chem. Phys.96, 7542 (1992).
16.
LianL.SchultzR.H. and ArmentroutP.B. (unpublished results).
17.
HalesD.A.LianL. and ArmentroutP.B., Int. J. Mass Spectrom. Ion Processes102, 269 (1990).
18.
LohS.K.LianL. and ArmentroutP.B., J. Am. Chem. Soc.111, 3167 (1989).
19.
HalesD.A., CID of Transition Metal Cluster Ions. Ph.D. Thesis, University of Utah. Utah, USA, 204 pp. (1990).
20.
ArmentroutP.B.HalesD.A. and LianL., in Advances in Metal and Semiconductor Clusters, Vol. II, Ed by DuncanM.A.JAI, Greenwich, CT, USA, p. 1. (1994).
21.
ArmentroutP.B., in Metal-Ligand Interactions—Structure and Reactivity, Ed by RussoN. and SalahubD.R.Kluwer-Academic Publishers, Dordrecht, Germany, p. 23 (1996).
22.
ArmentroutP.B.GriffinJ.B. and ConceiçãoJ., in Progress in Physics of Clusters, Ed by ChuevG.N.LakhnoV.D. and NefedovA.P., World Scientific, Singapore, p. 198 (1999).
23.
MiedemaA.R., Z. Metallkunde69, 287 (1978).
24.
MiedemaA.R., Faraday Symp. Royal Soc. Chem.14, 136 (1980).
25.
GriffinJ.B. and ArmentroutP.B., J. Chem. Phys.106, 4448 (1997).
26.
GriffinJ.B. and ArmentroutP.B., J. Chem. Phys.108, 8062 (1998).
27.
XuJ.RodgersM.T.GriffinJ.B. and ArmentroutP.B., J. Chem. Phys.108, 9339 (1998).
28.
VardhanD.LiyanageR. and ArmentroutP.B., J. Chem. Phys.119, 4166 (2003).
29.
GriffinJ.B. and ArmentroutP.B., J. Chem. Phys.107, 5345 (1997).
30.
GriffinJ.B. and ArmentroutP.B., J. Chem. Phys.108, 8075 (1998).
31.
ConceiçaoJ.LohS.K.LianL. and ArmentroutP.B., J. Chem. Phys.104, 3976 (1996).
32.
ConceiçaoJ.LiyanageR. and ArmentroutP.B., Chem. Phys.262, 115 (2000).
33.
LiyanageR.ConceiçaoJ. and ArmentroutP.B., J. Chem. Phys.116, 936 (2002).
34.
LiuF.LiyanageR. and ArmentroutP.B., J. Chem. Phys.117, 132 (2002).
35.
LiyanageR.ZhangX-G. and ArmentroutP.B., J. Chem. Phys.115, 9747 (2001).
36.
ArmentroutP.B., Ann. Rev. Phys. Chem.52, 423 (2001).
37.
DeitzT.G.DuncanM.A.PowersD.E. and SmalleyR.E., J. Chem. Phys.74, 6511 (1981).
38.
LohS.K.HalesD.A. and ArmentroutP.B., Chem. Phys. Lett.129, 527 (1986).
39.
TeloyE. and GerlichD., Chem. Phys.4, 417 (1974); GerlichD., Adv. Chem. Phys.82, 1 (1992); GerlichD., in State-selected and State-to-state Ion-Molecule Reaction Dynamics, Ed by NgC.-Y. and BaerM.John Wiley & Sons Inc., New York, USA, p. 1 (1992).
40.
ErvinK.M. and ArmentroutP.B., J. Chem. Phys.83, 166 (1985).
41.
DalyN.R., Rev. Sci. Instrum.31, 264 (1959).
42.
ChesnavichW.J. and BowersM.T., J. Phys. Chem.83, 900 (1979).
43.
ArmentroutP.B., in Advances in Gas Phase Metal Ion Chemistry, Vol. 1, Ed by AdamsN.G. and BabbockL.M.JAI, Greenwich, CT, USA, p. 83 (1992).
44.
ArmentroutP.B., Int. J. Mass Spectrom.200, 219 (2000).
45.
ShvartsburgA.A.ErvinK.M. and FrederickJ.H., J. Chem. Phys.104, 8458 (1996).
46.
GilbertR.G. and SmithS.C., Theory of Unimolecular and Recombination Reactions, Blackwell Scientific, Oxford, UK (1990).
47.
HolbrookK.A.PillingM.J. and RobertsonS.H., Unimolecular Reactions, 2nd Edn.John Wiley & Sons Inc., New York, USA (1996).
48.
TruhlarD.G.GarrettB.C. and KlippensteinS.J., J. Phys. Chem.100, 12771 (1996).
49.
RodgersM.T.ErvinK.M. and ArmentroutP.B., J. Chem. Phys.106, 4499 (1997).
50.
KrennG.EiblC.MauritschW.HebenstreitE.L.D.VargaP. and WinklerA., Surf. Sci.445, 343 (2000).
51.
BeutlM.LesnikJ.LaundgrenE.KonvickaC.VargaP. and RendulicK.D., Surf. Sci.447, 245 (2000).
52.
ToyoshimaI. and SomorjaiG., Catalysis Rev. Sci. Eng.19, 105 (1979).
53.
FreseK.W., Surf. Sci.182, 85 (1987).
54.
BoszoF.ErtlG.GrunzeM. and WeissM., Appl. Surf. Sci.1, 103 (1977).
55.
BoszoF.ErtlG. and WeissM., J. Catal.50, 519 (1977).
56.
BenzigerJ.B., in Metal-Surface Reaction Energetics, Ed by ShustorovichE.VCH, New York, USA, p. 53 (1991).
57.
ChristmannK.BehmR.J.ErtlG.Van HoveM.A. and WeinbergW.H., J. Chem. Phys.70, 4168 (1979).
58.
ChristmannK.SchoberO.ErtlG. and NeumanM., J. Chem. Phys.60, 4528 (1974).
59.
LapujouladeJ. and NeilK.S., J. Chem. Phys.57, 34 (1972).
60.
BrennanD.HaywardD.O. and TradnellB.M.W., Proc. Roy. Soc.A256, 81 (1960).
61.
BraggJ. and TomkinsT.C., Trans. Faraday Soc.51, 1071 (1955).
62.
WedlerG., Z. Phys. Chem.27, 388 (1961).
63.
BenzigerJ.B. and PrestonR.E., Surf. Sci.141, 576 (1984).
64.
BrownW.A.KoseR. and KingD.A., Chem. Rev.98, 797 (1998).
65.
HaynesC.L.ChenY.-M. and ArmentroutP.B., J. Phys. Chem.100, 111 (1996).
