Geometry and Electronic Properties of Glycerol Adsorbed on Bare and Transition-Metal Surface-Alloyed Au(111): A Density Functional Theory Study.

Quantum chem. calcns. were performed to validate a range of dispersion-cor. functionals to accurately predict and interpret structural, electronic, and vibrational properties of glycerol adsorbed on bare and transition-metal surface-alloyed Au(111) surface. The optB86b-vdW (van der Waals) was found to have the overall best agreement with expts. concerning lattice const., bulk stress, surface energy, and methanol adsorption among PBE (Perdew-Burke-Ernzerhof), optB88-vdW, optPBE-vdW, vdW-DF (d. functional), vdW-DF2 (d. functional 2nd version), and vdW-BEEF (Bayesian error estn. functional). Glycerol adsorption energy is found to correlate well with the calcd. d-band center of the transition-metal-contg. Au(111) surface layer. O-H stretching vibrations are found to be very sensitive of the surface-alloy atom and resulted in large shifts toward lower wavenumbers, when compared to those on bare Au(111). The latter results clearly show that adsorption of glycerol to surface-alloy atoms can be monitored in situ by IR spectroscopy. [on SciFinder(R)]