The functional relationships between the basic characteristics of individual bands of electronic and vibrational spectra of free polyatomic molecules are ascertained. These basic characteristics are the position of the maximum of an individual electronic-vibrational band, the rate of the temperature shift of the maximum of a band, the half-width of a homogeneously or heterogeneously broadened electronic-vibrational band, the rate of the temperature variation of the half-width of a band, the asymmetry parameter of a heterogeneously broadened band, and the conditions for symmetric or asymmetric distribution of the intensity over the contour of a spectral band. The interrelations between the basic spectral characteristics result from the sequential mechanism of formation and broadening of individual bands of electronic and vibrational spectra of free polyatomic molecules. It is shown that the investigation of the basic spectral characteristics of electronic-vibrational bands and their interrelations allows one to elucidate the nature of the internal motion determining the optical properties of polyatomic molecules.
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