Adsorption geometry and core excitation spectra of three phenylpropene isomers on Cu(111)

C. KOLCZEWSKI; F. J. WILLIAMS; R. L. CROPLEY; O. P. H. VAUGHAN; A. J. URQUHART; M. S. TIKHOV; R. M. LAMBERT; K. HERMANN

JOURNAL OF CHEMICAL PHYSICS

AMER INST PHYSICS

Año: 2006 vol. 125 p. 34701 - 34710

0021-9606

Theoretical C 1s near edge x-ray absorption fine structure NEXAF spectra for the C9H10 isomers trans-methylstyren-methylstyrene, and allylbenzene in gas phase and adsorbed at C111 surfaces have been obtained from density functional theory calculations where adsorbate geometries were determined by corresponding total energy optimizations. The three species show characteristic differences in widths and peak shapes of the lowest C 1s* transitions which are explained by different coupling of the electron system of the C6 ring with that of the side chain in the molecules as well as by the existence of nonequivalent carbon centers. The adsorbed molecules bind only weakly with the substrate which makes the use of theoretical NEXAFS spectra of the oriented free molecules meaningful for an interpretation of experimental angle-resolved NEXAFS spectra of the adsorbate systems obtained in this work. However, a detailed quantitative account of relative peak intensities requires theoretical angle-resolved NEXAFS spectra of the complete adsorbate systems which have been evaluated within the surface cluster approach. The comparison with experiment yields almost perfect agreement and confirms the reliability of the calculated equilibrium geometries of the adsorbates. This can help to explain observed differences in the catalytic epoxidation of the three molecules on Cu111 based on purely geometric considerations.