Abstract
The dynamics of excited atom interactions with other atoms, which often lead to associative ionization, is largely governed by stochastic diffusion of the valence electron through Rydberg states prior to the ionization. Such processes are associated with random changes of the energy state of the highly excited electron, and they are likely to influence the nuclear dynamics, especially at subthermal collision energies. Possibilities of manipulation of the chaotic dynamics of Rydberg states require a detailed exploration. For an electron in a given Rydberg state moving in a microwave field, which can be generated via interaction with another atom or molecule, there exists critical field strength, above which motion of the electron in the energy space is chaotic. Recently a way to block the dynamic chaos regime was shown, if a given Rydberg state is located somewhat above the middle between the two other states with the orbital quantum number differing by one, whereby level shifts can be controlled by employing Stark/Zeeman shifts in external DC electric/magnetic fields. The stochastic effects in collisions involving Rydberg particles, in which the initial and final reaction channels are connected via intermediate highly excited collision complexes with multiple crossings of energy levels, can be treated using the dynamic chaos approach (Chirikov criterion, Standard and Keppler mapping of time evolution of the Rydberg electron, solution of the Fokker-Plank- and Langevin-type of equations, etc.). Such approach to obtaining dynamics characteristics is a natural choice, since the treatment of Rydberg electron dynamics as a kind of diffusion process allowing one to bypass the multi-level-crossing problem, which can hardly be solved by conventional quantum chemistry methods.
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