461983 Adsorption of Hetero-Bifunctional Urea on Ge(100)-2x1 Surface
Density functional theory (DFT) calculations suggest that NH2 dissociation is the most thermodynamically favorable pathway for the single reaction. The reaction can occur through two possible precursor states: a nitrogen dative bond with the surface or an oxygen dative bond that can further undergo an enolization reaction. Interestingly, the oxygen dative bond is 7 kcal/mol more stable than the nitrogen bond, suggesting a preference for the latter reaction pathway. Furthermore, calculations show that the dual reactions provide less stabilization gain and a higher kinetic cost than single reactions, as the dual NH2 dissociation has an activation barrier greater than 30 kcal/mol and only provides 5 kcal/mol of additional exothermicity, indicating that the urea molecule will likely react only through a single functional group. X-ray photoelectron spectroscopy (XPS) and multiple internal reflection Fourier transform infrared (MIR-FTIR) spectroscopy were used to determine the final reaction products. Results suggest that urea adsorbs on Ge(100) forming a mix of surface products. One of the products can be identified by the downshift in binding energy of the N(1s) XP peak and the Ge-H stretching mode in IR as NH2-dissociated urea on Ge. This assignment is also consistent with the presence of a carbonyl group in the IR and XPS spectra, which is expected to remain unchanged in this surface configuration. Another reaction product exists that is evident by second O(1s) and C(1s) XPS peaks downshifted from that of the parent urea molecule, suggesting a loss of the carbonyl group by a reaction with a more electropositive atom. Moreover, coverage results support our DFT findings by suggesting that each urea molecule will occupy a Ge dimer by reacting through a single functional group per molecule.