Atoms and molecules in highly excited (Rydberg) states have a number of unique characteristics due to the strong dependence of their properties on the values of principal quantum numbers. The paper discusses the results of an investigation of collisional Rydberg complexes specific features, resulting in the development of dynamic chaos and the accompanying diffusion autoionization processes. It is shown (experiment and theory) that, in subthermal low energies, the global chaotic regime that evolved in quasimolecular systems leads to significant changes in the Rydberg gases radiation/ionization kinetics. The effect of Förster resonance on the width of the fluorescence spectra and stochastic ionization processes in Rydberg systems is also discussed.