Abstract
The intensity distribution, the spectral band profile, and the temperature dependences of spectral characteristics of bands in the electronic-vibrational (vibronic) spectra of free polyatomic molecules are studied based on the concept of sequential lines (SLs) as constituent elements of these bands. It is shown that the intensity distribution in a separate electronic-vibrational band is defined by the convolution of an SL profile with the frequency distribution function of sequential transitions. Expressions for the intensity distribution in homogeneously and inhomogeneously broadened electronic-vibrational bands are derived, and specific features of their spectral behavior are determined. Using the latter results, distinguishing features or criteria of the character of broadening of the vibronic spectra of free polyatomic molecules are formulated.
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