A density functional model for tuning the charge transfer between a transition metal electrode and a chemisorbed molecule via the electrode potential

A simple approach is proposed to predict the magnitude of charge transfer b etween a polarized transition metal electrode and a chemisorbed molecule in an electrolytic solution. The approach is based on the equalization of the chemical potentials, as defined in density-functional theory (DFT). The sy stem is modeled by a metal cluster, a molecule, and a set of point charges (counter ions) and the properties evaluated using methods derived from DFT; specifically, we study here the chemisorption of acrylonitrile on nickel. This approach allows us to point out the various factors determining the ch arge transfer. The results show a linear increase in the amount of charge t ransferred to the chemisorbed molecule with the polarization of the metal e lectrode. (C) 2001 American Institute of Physics.