The potential （E）-dependent vibrational behavior of a saturated CO adlayer on Au-core Pd-shell nanoparticle film electrodes was investigated over a wide potential range, in acidic, neutral, and basic solutions, using in situ surface-enhanced Raman spectroscopy （SERS）. Over the whole of the examined potential region （-1.5 to 0.55 V vs. NHE）, the peak frequencies of both the C-OM and the Pd-COM band （here, M denotes the multiply-bonded configuration） displayed three distinct linear regions： dvc oM/dE decreased from -185-207 （from -1.5 to -1.2 V） to -83-84 cm-1/V （-1.2 to -0.15 V）, and then to 43 cm-1/V （-0.2 to 0.55 V）; on the other hand, dvpd coM/dE changed from -10 to -8 cm I/V （from -1.5 to -1.2 V） to ^-31 to -30 cm-1/V （-1.2 to -0.15 V）, and then to -15 cm-1/V （-0.2 to 0.55 V）. The simultaneously recorded cyclic voltammograms revealed that at E 〈 -1.2 V, a hydro- gen evolution reaction （HER） occurred. With the help of periodic density functional theory calcula- tions using two different （2 × 2）-3CO slab models with Pd（111）, the unusually high dvc-oM/dE and the small dVPd-CoM/dE in the HER region were explained as being due to the conversion of COad from bridge to hollow sites, which was induced by the co-adsorbed hydrogen atoms formed from dissociated water at negative potentials.
