THEORETICAL-ANALYSIS OF THE PHOTOINDUCED ELECTRON-TRANSFER IN PORPHYRIN QUINONE CYCLOPHANES

Quantum calculations of the INDO-S/CI type are performed on a porphyrin-quinone cyclophane complex to determine the molecular parameters which govern the photoinduced charge separation, such as energy locations of the excited state and the lowest charge transfer states as well as the electron transfer couplings. From the molecular dynamics studies, the structural arrangement of the quinone relative to the porphyrin and the reorganization energies of the solvents are extracted. The results are cast in analytic form, which shows explicitly the polarity dependence of the solvent-induced intramolecular electron transfer process. The theory is used to interpret experimental results in a companion paper.