Abstract
A steric effect has been identified and measured in the interaction of electrons with oriented molecules, for the first time. Photoelectron mediated reactivity has been determined, with a cross section of σ = (3.0 ± 0.4) × 10-19 cm2 (methyl down) for an adsorbed CD3Br on O/Ru(001). A three times smaller cross section was obtained for the bromine down configuration, controlled by oxygen precoverage. A qualitatively similar molecular orientation dependent effect was measured by direct bombardment with 10 eV electrons, however, at much larger cross sections. The significance of the steric effect reported here for electron-transfer processes in general is discussed.
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