Ab initio study of the electrochemical polymerization mechanism of omega-diamines

The anodic oxidation of liquid omega -diamine based-electrolyte leads to th e passivation of the electrode surface by an insulating film as shown by us ing an electrochemical quartz crystal microbalance (EQCM) coupled with cycl ic voltammetry (CV) technique. These films were identified by infrared-atte nuated total reflectance (IR-ATR) as polymeric films: linear polyethylenimi ne (L-PEI) film for EDA based-electrolyte and linear propylenimine (L-PPI) for 1,3 DAP. We also performed computations of energy and thermochemical va lues with the quantum-chemical Onsager self-consistent reaction field (SCRF ) method at the Hartree-Fock level for modeling the reaction mechanisms lea ding to the polymeric films. (C) 2001 American Institute of Physics.