Journal of Physical Chemistry, Vol.98, No.39, 9750-9763, 1994
Exciton, Exchange, and Through-Bond Interactions in Multichromophoric Molecules - An Analysis of the Electronic Excited-States
Electronic excitation spectra of rigidly bridged aromatic chromophores (naphthalene and perylene) are analyzed with the help of WDO/S-SCI calculations. The interactions between the chromophores, with varying mutual orientation, are interpreted in terms of exciton, exchange, and through-bond interactions. Electronic spectra of naphthalene, perylene, and tetranaphthylene are presented. Symmetries of excited states up to an energy of 65 000 cm(-1) are derived from the polarized luminescence and excitation spectra. Phosphorescence spectra of naphthalene and tetranaphthylene are interpreted as due to triplet-excimer formation. Monomer spectra are used to analyze the computed spectra of covalently linked chromophores. It has been shown that INDO/S computations give excellent results that would be helpful to interpret the electronic spectra of multichromophoric molecules.
Keywords:DIPOLE-FORBIDDEN TRANSITIONS;2-PHOTON SPECTROSCOPY;AROMATIC-HYDROCARBONS;PORPHYRIN DIMERS;SPECTRA;NAPHTHALENE;FLUORESCENCE;ABSORPTION;RELAXATION;COMPONENTS