Optical second harmonic generation at platinum phthalocyanine-modified platinum electrodes

Optical second harmonic generation (SHG) has been used to observe changes within electronically conducting platinum phthalocyanine (PtPc) films deposited on polycrystalline platinum electrodes as the film undergoes electrochemical modification. PtPc-modified electrodes produced enhanced SHG responses over bare platinum surfaces. This is proposed to be due to an electric quadrupole contribution from the PtPc molecule. Examination of the polarization dependence of the SHG response reveals that electroactive PtPc molecules exist in environments both parallel and perpendicular to the electrode surface. It has been possible to observe redox processes occurring within the films by monitoring the magnitude of the SHG response with variations in potential. The decrease in SHG signal has been shown empirically to be proportional to the charge removed from the film during oxidation of the phthalocyanine (Pc) ring.