Multiple Fermi Resonances in Liquid Benzene
A number of coupled Fermi vibrational resonances (FRs) in liquid benzene from a multitude of them are systematically studied. The spectral structure of the vibrational bands in the IR absorption and Raman scattering spectra are determined by their numerical decomposition into individual components. The complication of vibrational resonances with an increase in their order is due to the overlapping of FRs and the appearance of additional resonant vibrational modes. To clarify the identification of the vibrations of the benzene FR v1+v6, v8 and the correction of the frequencies of a number of inactive vibrations, including v13(E1u), the experimental results are compared to the data obtained by quantum-chemical calculations. With regard for the collective-wave properties of vibrational modes in the benzene liquid state, we propose a new content of the analysis of FRs. It should include the study of 1) the intensity changes for various spectral components in the IR absorption and Raman scattering for FR vibrational bands of various orders, 2) half-widths δv of the bands, and 3) anharmonic shifts ΔvA for various components in the vibrational bands of FRs.
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