Cyanide adsorbed on coinage metal electrodes: A relativistic density functional investigation
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The adsorptive properties of cyanide (CN-) on coinage metal (M) electrodes (M = Cu, Ag, Au) have been investigated using a relativistic density functional method. The way to model the electrochemical potential applied to the electrodes is to consider the systems in the presence of a perturbative external field F. The field-perturbative approach is proven to be a suitable method in interpreting the observed spectral shifts with electrode potential. The calculated potential-dependent shifts of omega(M-CN) and omega(C-M) are similar for the three metals, in agreement with experiment observations. The relativistic effects are required to account for the similarity in the frequency shifts of omega(M-CN). The calculated vibrational tuning rates d omega(C-N)/dF are 6.61 x 10(-7), 6.61 x 10(-7), and 5.64 x 10(-7) cm(-1)/(V/cm) for M = Cu, Ag, and Au, respectively. The coupling of the M-CN and C-N internal modes contributes significantly (about 25%) to the size of the frequency shifts Delta omega(C-N) of the ligand. The effect of electric fields on the metal-CN- bonding is also investigated. It is shown that changes in the magnitude of CN- to the metal donation and M-CN bond strength occur under the influence of the electric field. (C) 1998 John Wiley & Sons, Inc.
CitationINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY，1998,67（3）：175-185