Quantum chemistry studies on electronic properties of CN − adsorbed on silver electrodes

Abstract

The electronic properties of CN − adsorbed on Ag electrodes at different potentials have been studied by using the method of self-consistent-charge discrete variational Xα (SCC-DV-Xα) cluster calculations. It is shown that the binding of −NCAg is dominated by both electrostatic and polarization effects derived from the charge of CN −, and that the transfer of σ charge from CN − to silver is the largest donation contribution. The electrode potential influences this charge transfer process and the interaction between CN − adsorbate and silver electrode. The results of quantum chemistry calculations fit well with the experimental data of in situ spectroscopic studies on the CN −/Ag electrode systems.