Manifestation of the vibronic analogue of the Fermi resonance in quasi-line spectra of porphyrins: Experiment and theoretical analysis

The quasi-line low-temperature (4.2 K) fluorescence excitation spectra of two porphyrins, meso-tetraazaporphin and meso-tetrapropylporphin introduced into an n-octane matrix are measured in the range of the S ₀ → S ₂ electronic transition. A characteristic feature of these spectra is that a conglomerate of quasi-lines—a structured complex band—is observed instead of one 0–0 quasi-line of the S ₀ → S ₂ transition. In this band, the intensity distributions for the two main types of impurity centers considerably differ from each other. The occurrence of such conglomerates is interpreted as a result of nonadiabatic electronic-vibrational interactions between vibronic S ₂ and S ₁ states (the complex vibronic analogue of the Fermi resonance). The frequencies and intensities of individual transitions determined from the deconvolution of complex conglomerates are used as the initial data for solving the inverse spectroscopic problem: the determination of the unperturbed electronic and vibrational levels of states involved in the resonance and the electronic-vibrational interaction matrix elements between them. This problem is solved with a method developed previously. The energy intervals between the S ₂ and S ₁ electronic levels of the two main types of impurity centers formed by molecules of a given porphyrin in the crystal matrix are found to significantly differ from each other (～100 cm^?1). At the same time, the energies of the unperturbed vibrational states of the S ₁ electronic level partcipating in the resonance are very close to each other for these two types of impurity centers.