The mechanism of electroreduction of silver cyanide complexes in aqueous electrolytes—II. Interpretation of SERS data

✍ Scribed by V. Daujotis; V. Kairys

• Book ID: 104114988
• Publisher: Elsevier Science
• Year: 1997
• Tongue: English
• Weight: 641 KB
• Volume: 42
• Category: Article
• ISSN: 0013-4686
• DOI: 10.1016/s0013-4686(96)00288-5

✦ Synopsis

Time dependencies of the intensities and FWHM of the adsorbed cyanide Raman stretching band correlate with the features of the time dependencies of electron numbers obtained from EQCM measurements. Quantum-chemical ab inifio calculations show that the excitation wavelength of about 765 nm excites electron transitions between the [Ag+-CN-] states, whose quadrupole moments differ greatly. The earlier measured maxima in Raman excitation profiles for different adsorbates roughened silver surface the following ;;~Ru~O~(NH;),#+)

-590 < triphenylphadsephinr-620 nm < pyridine order (nm): ruthenium red -720 < cyanide which coincides with the decrease in size of these molecules. The contribution due to the excitation in the Ad cluster is larger when the adsorbate is smaller because of the more closely localized vibrational modes whereas contribution to the Raman scattering enhancement due to the excitation of surface plasma oscillations in the macroscopic silver clusters is constant.