Abstract

Recent field ionization measurements of various high-n molecular Rydberg states doped into argon, krypton and xenon perturbers are presented as a function of perturber number density up to the density of the triple point liquid. These data are modeled to within ±0.3% of experiment on both critical and noncritical isotherms using a new theoretical treatment that includes: (i) the polarization of the perturber by the dopant cation, (ii) the polarization of the perturber by the quasi-free electron that arises from field ionization of the dopant, and (iii) the kinetic energy of the quasi-free electron. The polarization terms are determined by a standard statistical mechanical treatment. However, the kinetic energy of the quasi-free electron is calculated within a new local Wigner–Seitz model that contains only one adjustable parameter. This treatment provides an accurate model of the energy of the bottom of the conduction band (V0) in argon, krypton and xenon from the dilute gas up to the density of the triple point liquid, on both critical and noncritical isotherms.

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