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We study various physical mechanisms of electron-ion recombination accompanied by the formation of Rydberg atoms in plasmas containing atomic and molecular ions. Analytical approach to the description of resonant mechanism of ternary electron capture associated with the non-adiabatic energy transfer from free electron to the electronic shell of a quasimolecular ion is developed. Similar technique is used for the evaluation of the integral contribution of all rovibrational states of a bound molecular ion to the Boltzmann-averaged cross section and rate constant of dissociative recombination (DR). Simple expressions for cross sections and rate constants of non-resonant electron capture to Rydberg states in ternary electron-ion-atom collisions are derived in the impulse approximation. We perform a comparative analysis of the efficiencies of resonant and non-resonant three-body recombination of electrons with atomic ions and DR of molecular ions in plasmas of rare gas mixtures, Rg/Xe, with small relative concentration of xenon ([Xe]=[Rg], Rg=He, Ne, Ar, Kr). It is shown that in a wide range of plasma parameters the resonant recombination mechanisms are predominant. The behavior and magnitudes of the recombination rate constants turn out to be quite different for heteronuclear ions with small (HeXe + and NeXe + , D 0 =13.1 and 33 meV) and moderate (ArXe + and KrXe + , D 0 = 171 and 400 meV) values of the dissociation energy.

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