ENERGETICS AND KINETICS OF ETHYLBENZENE ADSORPTION ON EPITAXIAL FEO(111) AND FE3O4(111) FILMS STUDIED BY THERMAL-DESORPTION AND PHOTOELECTRON-SPECTROSCOPY

The adsorption of ethylbenzene (EB) has been studied on thin films of FeO(III) and Fe3O4(III) grown epitaxially on Pt(lll) using thermal des orption spectroscopy (TDS), ultraviolet photoelectron spectroscopy (UP S) and low energy electron diffraction (LEED). Applying a threshold an alysis of the TDS data, desorption energies E-des and the correspondin g frequency factors are deduced. The UPS measurements are performed un der adsorption-desorption equilibrium conditions: The spectra are take n at varying sample temperature at constant EB gas phase pressures. Fr om the spectra, the EB-coverages theta(EB) are deduced. From the adsor ption isobars obtained in this way, isosteric heats of adsorption q(st )(theta(EB)) are obtained which are compared to the desorption energie s E-des deduced from TDS. On the oxygen-terminated FeO(III) surface, t wo adsorption states are observed, a physisorbed first layer (beta-EB) followed by condensation (alpha-EB). Their UP spectra are almost iden tical and very similar to the spectrum of gas phase EB. On Fe3O4(III), a more strongly chemisorbed species (gamma(1)-EB) is adsorbed first, followed by physisorbed beta- and condensed alpha-EB. The chemisorbed phase exhibits a strong shift and split of the highest occupied pi orb itals of the phenyl group. This indicates a strong interaction between the substrate and the adsorbed molecules that are adsorbed with the p henyl ring lying flat on the surface. The desorption energies E-des an d the isosteric heats of adsorption q(st), respectively, are 91 (85) k J/mol for gamma(1)-, 55 (58) KJ/mol for beta- and 50 (52) kJ/mol for a lpha-EB and agree generally well. The differences are discussed in ter ms of different coverage ranges accessible for both methods, the noneq uilibrium character of the TDS method and to the threshold analysis wh ich yields only data for the most loosely bound molecules desorbing fi rst in each desorption track. (C) 1998 American Institute of Physics.