IR STUDIES OF CHEMISORPTION ON MOLECULAR SURFACES: AMMONIA ON SILVER CLUSTERS

D.M. Rayner, L. Lian, K. Athanassenas, B.A. Collings, R. Fournier, S.A. Mitchell and P.A. Hackett
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D.M. Rayner: Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario, Canada K1A 0R6, Canada
L. Lian: Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario, Canada K1A 0R6, Canada
K. Athanassenas: Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario, Canada K1A 0R6, Canada
B.A. Collings: Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario, Canada K1A 0R6, Canada
R. Fournier: Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario, Canada K1A 0R6, Canada
S.A. Mitchell: Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario, Canada K1A 0R6, Canada
P.A. Hackett: Steacie Institute for Molecular Sciences, National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario, Canada K1A 0R6, Canada

Surface Review and Letters (SRL), 1996, vol. 03, issue 01, 649-654

Abstract: Metal clusters are proposed as models to develop a molecular perspective on surface processes and to increase our understanding in important areas such as heterogeneous catalysis. This goal requires the characterization of small metal-cluster-ligand complexes in as great detail as possible. One avenue is to apply IR spectroscopy to cluster-ligand complexes. Problems of number density and mass selectivity prohibit the use of direct optical absorption methods. We report on progress towards applying infrared multiphoton dissociation, IRMPD, to obtain spectra by direct photodepletion. In this regard the silver-cluster-ammonia system is promising. The action spectrum for IRMPD ofAg2NH3, monitored via theAg2product in a fast-flow reactor, reveals an absorption peak at1065cm−1which is assigned to the−NH3umbrella mode of the complex. Molecular structure calculations using density-functional theory predict an end-on geometry and are in good agreement with this value. Preliminary results on complexes of largerAgclusters studied by monitoring the IRMPD depletion of aAgnNH3molecular beam by time-of-flight mass spectrometry are presented. The promise of these systems as models forNH3bound toAgsurfaces is discussed.

Date: 1996
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DOI: 10.1142/S0218625X96001169

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