LOCAL EXCITATIONS IN STATISTICAL SYSTEMS, DYNAMICS AND SUPERCOLLISIONAL EFFECTS

Classical and quantum statistical expressions are given for the probab ility of finding large quantities of energy, E', in a small moiety, wh ich might be a collision site, of a highly excited polyatomic molecule in which the internal energy, E, is statistically distributed. Also g iven are expressions for the rate coefficients for moving E', out of t otal E, into the moiety. Probabilities of finding E' above 10000 cm-1, 16000 cm-1 or 20000 cm-12 in an azulene molecule with internal energy of 30000 cm-1 are reported. The findings explain a prerequisite for s upercollisions namely, the presence of large quantities of energy in a collision site from which it is then removed by a supercollision.