Electric field-induced shifts of vibrational frequencies of CO adsorbed on Ni, Pd, Pt, Cu, Ag and Au metal (100) surfaces A theoretical comparative study

Abstract

A theoretical comparative study of electric field(F)-induced vibrational frequency shifts of CO adsorbed on Ni, Pd, Pt, Cu, Ag and Au metal (100) surfaces is presented. The calculated vibrational tuning rates dω_C–O/dF for the various metals are similar, thereby corroborating the experimental results of Ikezawa etal. The calculated absolute values are close to Lambert's observed values for CO on Ni in ultrahigh vacuum (UHV). The resulting estimates of the vibrational tuning rate with potential V are in qualitative agreement with experimental data in aqueous electrolytes. The small experimental value of tuning rate for CO on Pt in UHV is not supported by the calculation. The M–CO bonding properties and their trends among the metals are also investigated.