The reactions of silver clusters with ethylene and ethylene oxide:: Infrared and photoionization studies of Agn(C2H4)m, Agn(C2H4O)m and their deuterated analogs

被引:73
作者
Koretsky, GM [1 ]
Knickelbein, MB [1 ]
机构
[1] Argonne Natl Lab, Div Chem, Argonne, IL 60439 USA
关键词
D O I
10.1063/1.474219
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Ethylene and ethylene oxide react readily with silver clusters at 70 K to form the addition complexes, Ag-n(C2H4), and Ag-n(C2H4O)(m), respectively. The infrared photodissociation spectra of Ag-n(C2H4)(m) and Ag-n(C2D4)(m) (n = 3-7) recorded in the 9-11 mu m region show several characteristic vibrational bands of ethylene lying near their gas phase frequencies. Photoionization spectroscopy studies reveal that the ionization potentials (IPs) of the complexes decrease monotonically with adsorption of additional ethylene molecules. Together, these results imply that as on macroscopic Silver surfaces, ethylene adsorbs molecularly to small silver clusters, with a net donation of electron density into the underlying cluster. Similarly, silver cluster-ethylene oxide complexes display IPs that decrease with increasing adsorbate coverage. The infrared depletion spectra of Ag-n(C2D4O)(m) complexes reveal a single feature at 949 cm(-1), assigned to the nu(4)(a(1)) fundamental of C2D4O. These results verify that ethylene oxide adsorbs molecularly to silver clusters, with the oxygen atom oriented toward the silver cluster. (C) 1997 American Institute of Physics.
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页码:10555 / 10566
页数:12
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