Adsorption energies, inter-adsorbate interactions, and the two binding sites within monolayer benzene on Ag(111) |
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Authors: | Rockey Thomas J Yang Minchul Dai Hai-Lung |
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Affiliation: | Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA. |
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Abstract: | The adsorption of monolayer and multilayer benzene on the Ag(111) surface was characterized using temperature programmed desorption (TPD). TPD spectra revealed two broad peaks at approximately 205 and approximately 150 K at submonolayer coverage and a sharper, multilayer peak at 140 K. Analysis of the coverage-dependent shape and shift of the two submonolayer peaks has resulted in their assignment to desorption from two different binding geometries on threefold-hollow sites with symmetries C(3v)(sigma d) and C(3v)(sigma v). The TPD peak analysis incorporated inter-adsorbate repulsive interaction that resulted from the local dipole moment at the adsorption site induced by the adsorbate-surface charge transfer bonding. The analysis has yielded desorption energies of 54.9 +/- 0.8 and 50.4 +/- 0.4 kJ/mol for the C(3v)(sigma d) and C(3v)(sigma v) configurations, respectively. The interface dipole and polarizability of the benzene-silver complex have been determined to be 5.4 +/- 1.8 D and 14 +/- 10 A3, respectively. Repulsive interactions in the monolayer were found to lower the desorption energy from the zero-coverage value by 14.8 kJ/mol. Leading edge analysis of the multilayer peak yielded a desorption energy of 40.9 +/- 0.7 kJ/mol. |
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