Chemisorption of acrylonitrile on the Cu(100) surface: A local density functional study

The possibility of chemically grafting polyacrylonitrile onto transition me tal electrodes via electropolymerization leads to promising applications in the fields of corrosion protection or metal surface functionalization. The initial step of the electrografting mechanism is the adsorption of the acr ylonitrile monomer on the metal surface from solution. Here, we investigate theoretically this adsorption process on the copper (100) surface; Density Functional Theory is used in the Local Spin Density approximation to descr ibe the electronic and structural properties of acrylonitrile adsorbed on c opper clusters. The chemisorption of acrylonitrile on the copper surface is confirmed experimentally via X-Ray Photoelectron Spectroscopy. The thermod ynamic characteristics of the adsorption process are also studied via stati stical mechanics. Finally, determining the influence of the copper cluster size on the adsorption of acrylonitrile allows to extrapolate the propertie s of the acrylonitrile/Cu(100) surface from those of acrylonitrile/copper c lusters. (C) 1999 American Institute of Physics. [S0021-9606(99)70231-X].