Energy of the quasi-free electron in argon, krypton and xenon

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 ( V 0 ) in argon, krypton and xenon from the dilute gas up to the density of the triple point liquid, on both critical and noncritical isotherms.