Spectroscopic studies of organometallic compounds on single crystal metal surfaces: Surface acetylides of silver (110)

Abstract The nature of compounds formed by the reaction of organic molecules with metal surfaces can be studied with a battery of analytical methods based on both physicals and chemical understanding. In this paper the application of UPS, XPS, LEED and EELS as well as temperature programmed reaction spectroscopy (TPRS) and chemical titration methods to the characterization of surface complexes is discussed. Particular emphasis is given to the reaction of acetylene with a single crystal surface of silver, Ag(110). Previous work has shown that this surface, when clean, is unreactive to hydrocarbons, alcohols and carboxylic acids under ultra high vacuum conditions. Preadsorption of oxygen, however, renders the surface reactive, and a wide variety of organometallic surface compounds can be formed. As expected then, no stable adsorption state and no reaction was observed with clean Ag(110) following room temperature exposure to acetylene. Following exposure at 150 K, however, a weekly bound chemisorption state was observed to desorb at 195 K, indicating a binding energy to the surface of approximately 12 kcal/gmole. Reaction with preadsorbed oxygen gave water formulation upon dosing and produced surface intermediates which yeilded two acetylene desorption states at 195 and 175 K. Heating above 300 K to completely desorb the higher temperature state produced new, well-defined LEED Features due to residual surface carbon which disappeared when the surface was heated above 550 K. Clearly, there were distinc changes in the nature of the absorbed layer at 195, 300 and 550 K. These changes were reflected in XPS. For the weakly chemisorbed acetylene a large C(ls) peak at 285.6 eV with a small, broad, indistinc shoulder at higher binding energy (288.2) was observed. The spectrum of the species following acetylene desorption at 275 K, however, showed the formulation of a large C(ls) peak at 283.6 eV in addition to peaks characteristics of the weakly chemisorbed state. This result indicated that the carbon atoms in the surface acetylide became inequivalent. Heating to 300 K produced a single peak at 282.8 eV which reverted to 283.4 when heated above 550 K; the carbon atoms became chemically equivalent. This latter state could be removed completely by O2 to form CO2(3). The XPS results showed quantitative conversion of all surface carbon from each state observed. Conclusive evidence regarding the identity of these states was obtained with titration experiments with deuterated acetic acid. CH3COOD was adsorbed on top of the acetylenic residues at 150 K and heated to note the isotopes of acetylene that desorbed. The 275 K acetylene desorption peak, which showed inequivalent carbon atoms, was titrated by CH3COOD to form C2HD, indicating C2H as the stable surface species. The species formed above 300 K, which showed equivalent carbon atoms in XPS, titrated to form C2D2, indicating a C2 surface species. In each case the formulation of surface acetate was quantitative. The structure of these species was probed further with high resolution electron energy loss spectroscopy. The weakly chemisorbed molecular state exhibited vibrational losses at 300, 700 and 3270 cm-1, characteristics of an acetylene-surface stretching motion, a C-C-H bend and the C-H stretch respectively. No C-C stretch was observed, indicating that the molecule lay parallel to the plane of the surface. For adsorbed C2H, bands were observed at 300, 690 and 3250cm-1. The high C-H stretching frequency indicated that the C-C bound order was near three. The absence of a C-C stretch in the spectrum was somewhat surprising, but was explained by a σ-π bonded complex in which the -C=CH species was flattened toward the surface by an interaction of an Ag atom with the π system of the acetylide.