Statistics of internal excitations of atomic systems

The character of internal excitations is compared for phase transitions and chemical transitions in atomic systems. Although the temperature dependences of some physical parameters of atomic systems have resonance-like structures with maxima in both cases, the dependences of the partition functions on the number of elementary excitations or the excitation energy differ because of the difference in the numbers of interactions that govern the transitions. The phase changes of condensed rare gases are considered in the case where the external pressure is small and the differences between phases are predominantly associated with differences in configurations. Important energy parameters of rare gases are determined by the attractive part of the pairwise interaction potential between atoms. The statistical analysis shows the existence of a “freezing limit” temperature for these systems, below which the liquid state becomes unstable. The kinetics of decay of such unstable states is analyzed in terms of the diffusion of voids.