Relaxation Processes at High Levels of Vibrational Excitation of Polyatomic Molecules in the Ground Electronic State

By the spectral and kinetic characteristics of the luminescence of vapors of polyatomic molecules (anthracene, anthraquinone, fluorenone) initiated by selective IR multiphoton excitation (IR MPE) of molecules in the ground electronic state S ₀ the relaxation processes proceeding under vibrational excitation of molecules to energies exceeding the energies of the lower excited electronic states have been investigated. The changes in the spectral and kinetic characteristics with increasing CO₂ laser energy density and vapor P _v and foreign gas pressure P _FG are analyzed. They are similar to the characteristics obtained for normal fluorescence of these molecules with changing vibrational energy E _vib content. On the basis of experimental data and model calculations it has been concluded that at the laser radiation densities used in the case of IR MPE the molecules reach energies considerably exceeding the energies of the electronic levels. It is shown that a nonadiabatic connection between the electronic states leads to the population of mixed electronic states isoenergetic to the vibrational levels of the ground electronic state and to emission of delayed luminescence spectrally identical to the normal luminescence of these molecules. It has been found that when high vibrational levels are populated, new relaxation channels, such as reverse electron relaxation, emission from high vibrational levels of the ground electronic state, and multiquantum vibrational energy transfer at collisions leading to a rapid establishment of vibrational equilibrium become important.