Density Functional Theory Calculations of Oxidation Potentials of Some Aromatic Hydrocarbons Derivatives in Acetonitrile

Density functional theory method at the level of B3LYP in combination with the polarizable continuum model have been used to compute one-electron oxidation potentials for fifteen different aromatic hydrocarbons derivatives in acetonitrile solution. A linear relation ship was observed between the the o retically predicted redox values and experimentally determined anodic peak potentials of the aromatic hydrocarbons derivatives. A good correlation is also found between experimental anodic peak oxidation potentials and a simple computed property, namely the energy of the high est occupied molecular orbital for neutral or radical cation of the aromatic hydrocarbons in acetonitrile (R2 = 0.95).