Elementary sequential spectral line and statistical properties of the thermal reservoir of free polyatomic molecules

The formation of vibronic spectra of free polyatomic molecules is studied by taking the concept of sequences as constituent elements of vibronic bands. Statistical properties of the thermal reservoir of oscillators, which randomly perturbs optically active transitions in a polyatomic molecule, are considered. The spectral shape, position, and width of the elementary sequential lines (ESL) are determined. It is shown that the ESLs have a Lorentzian shape if the perturbations are short-term and the pulse shape is symmetric about its origin. The position of the ESLs depends on the total vibrational energy of the thermal reservoir of oscillators in the initial electronic state of a molecule. The analysis of the statistical properties of the thermal reservoir of polyatomic molecules shows that one should distinguish between the ESL linewidth of individual molecules and the ESL linewidth averaged over the entire thermal ensemble. It is shown that individual molecules of the thermal ensemble that have different total vibrational energies are characterized by different widths of the ESLs. Consequently, the exchange and redistribution dynamics of the vibrational energy stored in the initial electronic state should manifest itself in the difference between the single-molecule ESL widths measured at different instants in time.