Reaction pathways of 2-iodoacetic acid on Cu(100): coverage-dependent competition between C-I bond scission and COOH deprotonation and identification of surface intermediates.

The chemistry of 2-iodoacetic acid on Cu(100) has been studied by a combination of reflection-absorption infrared spectroscopy (RAIRS), X-ray photoelectron spectroscopy (XPS), temperature-programmed reaction/desorption (TPR/D), and theoretical calculations based on density functional theory for the optimized intermediate structures. In the thermal decomposition of ICH(2)COOH on Cu(100) with a coverage less than a half monolayer, three surface intermediates, CH(2)COO, CH(3)COO, and CCOH, are generated and characterized spectroscopically. Based on their different thermal stabilities, the reaction pathways of ICH(2)COOH on Cu(100) at temperatures higher than 230 K are established to be ICH(2)COOH --> CH(2)COO + H + I, CH(2)COO + H --> CH(3)COO, and CH(3)COO --> CCOH.

Thermal decomposition of HSCH2CH2OH on Cu(111): identification and adsorption geometry of surface intermediates.

X-ray photoelectron spectroscopy has been employed to study the surface intermediates from the thermal decomposition of HSCH2CH2OH on Cu(111) at elevated temperatures. On the basis of the changes of the core-level binding energies of C, O, and S as a function of temperature, it is found that HSCH2CH2OH decomposes sequentially to form -SCH2CH2OH and -SCH2CH2O-. Theoretical calculations based on density functional theory for an unreconstructed one-layer copper surface suggest that -SCH2CH2OH is preferentially bonded at a 3-fold hollow site, with an adsorption energy lower than the cases at bridging and atop sites by 15.

Adsorption and reactions of ClCH2CH2OH on clean and oxygen-precovered Cu(100): experimental and computational studies.

Temperature-programmed reaction/desorption, reflection-absorption infrared spectroscopy, and density functional theory calculations have been employed to investigate the adsorption and thermal reactions of ClCH2CH2OH on clean and oxygen-precovered Cu(100) surfaces. On Cu(100), ClCH2CH2OH is mainly adsorbed reversibly. The ClCH2CH2OH molecules at a submonolayer coverage can change their orientation with increasing temperature.