OPTICAL-PROPERTIES OF POLYANILINE

Optical absorption has been used to study polyaniline at various levels of oxidation and protonation. The conversion of leucoemeraldine base to its salt accounts for the blue shift of the pi-pi* absorption from 3.94 to 4.17 eV. The emeraldine base has an absorption peak at 2.1 eV due to the localized benzenoid HOMO (highest occupied molecular orbital) to quinoid LUMO (lowest unoccupied molecular orbital) excitation. Protonation of the emeraldine base causes a lattice distortion of polyaniline to form a polaronic lattice structure, which accounts for the shift of the 2.1 eV absorption to 1.5 eV. Further protonation of emeraldine salt causes the breakdown of the polaronic lattice to a confined bipolaron lattice. When the acid strength of the solution is very high (96% H2SO4), most of the amine nitrogens are protonated. Characteristic absorptions of isolated quinoid imine units (approximately 2.5 eV) and benzene units (approximately 4.8 eV) have been found. The evolution of band structure corresponding to the optical-absorption change during the protonation of polyaniline at each specific oxidation state is studied by gradually changing the acid strength of the solution to which the polymer is subjected. We have also studied the optical-absorption change at one fixed acid strength by slowly oxidizing leucoemeraldine to emeraldine then to pernigraniline by electrochemical and chemical means. Detailed information has been obtained on the band structure changes in relation to lattice structure interconversions during the transitions between various oxidation and protonation states.