Abstract
The first reactive differential scattering study for atomic clusters is reported. Oxidation of Na x (x≦8) with O2 is investigated in a crossed beam apparatus. Sodium oxide (Na n O,n≦4) and sodium dioxide (Na n O2,n≦6) are produced with a total reactive cross section from 50 to 80 Å2, depending on the cluster size. The excess energies for these reactions are estimated by an SCF type ab initio calculation and range from 0.5 to 5 eV. The large cross section may then be understood quantitatively in terms of a harpooning mechanism as a first step in the reaction path. Angular distributions have been determined for the most abundant products, showing strong forward scattering. Two different schemes are discussed for the reaction: while the dioxides Na n O2 may be formed by an evaporative cooling process from a highly excited collision complex, formation of Na n O appears to originate from a direct process. In both cases the experimental data suggest that most of the exothermicity remains in the reaction products.
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de Heer, W.A., Knight, W.D., Chou, M.Y., Cohen, M.L.: Solid State Phys.40, 93 (1987)
Wang, C.R., Pollack, S., Kappes, M.M.: Chem. Phys. Lett.166, 26 (1990)
Knight, W.D., Clemenger, K., de Heer, W.A., Saunders, W.A., Chou, M.Y., Cohen, M.L.: Phys. Rev. Lett.52, 2141 (1984)
Martin, T.P., Bergmann, T., Göhlich, H., Lange, T.: Chem. Phys. Lett.172, 209 (1990)
Riley, S.J., Parks, E.K., Pobo, L.G., Wexler, S.: Ber. Bunsenges. Phys. Chem.88, 287 (1984)
Trevor, D.J., Whetten, R.L., Cox, D.M., Kaldor, A.: J. Am. Chem. Soc.107, 518 (1985)
Jarrold, M.F.: In: Bimolecular collisions, Ashfold, M.N.R., Baggott, J.E. (eds.). London: Royal Soc. Chem. (1989)
Peterson, K.I., Dao, P.D., Castleman, A.W. Jr.: J. Chem. Phys.79, 777 (1983)
Dao, P.D., Peterson, K.I., Castleman, A.W.: J. Chem. Phys.80, 563 (1984)
Lange, T., Göhlich, H., Näher, U., Martin, T.P.: Chem. Phys. Lett.192, 544 (1992)
Herschbach, D.R.: Faraday Discuss.33, 149 (1962); Birely, J.H., Hermn, R.R., Wilson, K.R., Herschbach, D.R.: J. Chem. Phys.47, 993 (1967); Miller, W.B., Safran, S.A., Herschbach, D.R.: Faraday Discuss.44, 108 (1967)
Goerke, A., Palm, H., Schulz, C.P., Spiegelmann, F., Hertel, I.V.: J. Chem. Phys.98, 9635 (1993)
Kappes, M.M., Schär, M., Röthlisberger, U., Yeretzian, C., Schumacher, E.: Chem. Phys. Lett.143, 251 (1988)
Dudourd, Ph., Rayane, D., Labastie, P., Pintar, B., Chevaleyre, J., Broyer, M., Wöste, L., Wolf, J.P.: J. Phys. IV C7, 509 (1991)
Bréchingnac, C., Cahuzac, Ph., Roux, J.Ph., Pavolini, D., Spiegelmann, F.: J. Chem. Phys.87, 5694 (1987)
Poteau, R., Spiegelmann, F.: Phys. Rev. B45, 1878 (1992)
Langhoff, S.R., Partrigde, H., Bauschlicher, C.W. Jr.: Chem. Phys.153, 1 (1991)
Schleyer, P.v.R., Würthwein, E.-U., Pople, J.A.: J. Am. Chem. Soc.104, 5839 (1982); Schleyer, P.v.R., Würthwein, E.-U., Kaufmann, E., Clark, T., Pople, J.A.: J. Am. Chem. Soc.105, 5930 (1983); Würthwein, E.-U., Schleyer, P.v.R., Pople, J.A.: J. Am. Chem. Soc.106, 6973 (1984)
Häser, M., Ahlrichs, R.: J. Comput. Chem.10, 104 (1989); Ahlrichs, R., Bär, M., Häser, M., Horn, H., Kölmel, C.: Chem. Phys. Lett.162, xx (1989)
Huzinaga, S.: Approximate atomic functions I, II. Alberta: University of Alberta (1971)
Magee, J.L.: J. Chem. Phys.8, 687 (1940)
Celotta, R.L., Bennet, R.A., Hall, J.L., Siegel, M.W., Levine, J.: Phys. Rev. A6, 631 (1972)
Goerke, A.: Dissertation, Albert-Ludwigs-Universität Freiburg (1993)
We have also measured the total scattering cross section by looking at depletion of the Na x intensity in the cluster beam after passing a gas cell. A preliminary evaluation of the data for O2 and N2 have shown, that the reactive part (as determined by the difference between the O2 and the N2 total cross section) are in the same range (50 to 120 Å2).
See e.g. Levine, R.D., Bernstein, R.B.: Molecular reaction dynamics and chemical reactivity. Oxford, New York: (1987)
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Goerke, A., Leipelt, G., Palm, H. et al. Reactive scattering of sodium clusters with molecular oxygen. Z Phys D - Atoms, Molecules and Clusters 32, 311–320 (1995). https://doi.org/10.1007/BF01437275
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DOI: https://doi.org/10.1007/BF01437275