Where Millimeter Wave Spectra are Sensitive to Small Electric Fields: High Rydberg States of Xenon and Their Hyperfine Structures

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Microwave

Scientific paper

In the range 0-45 cm^{-1} below the ionization limit, the separation between adjacent electronic states (Rydberg states with principal quantum number n>50) of atoms and molecules is smaller than 2 cm^{-1}. In order to resolve the fine or hyperfine structure of these states, it is necessary to combine high-resolution vacuum ultraviolet (VUV) laser radiation, which is required to access the Rydberg states from the ground state, with millimeter wave radiation. Such double-resonance experiments have been used to study the hyperfine structure of high Rydberg states of ^{83}Kr, H_2 or D_2. Millimeter wave transitions (240-350 GHz) between nℓ (52≤ n≤64, ℓ≤3) Rydberg states of different xenon isotopes were detected by pulsed field ionization followed by mass-selective detection of the cations. Because of the high polarizability of high-n Rydberg states (∝ n^7, ˜10^4 MHz cm^{2} V^{-2} for n≈ 50), it is necessary to reduce the electric stray fields to values of the order of mV/cm (or less) in order to minimize the (quadratic) Stark shift of the millimeter wave transitions. Some p and d Rydberg states of Xe are nearly degenerate and efficiently mixed by small stray fields, making it possible to observe transitions forbidden by the Δℓ=±1 selection rule or transitions exhibiting a linear Stark effect, which is typical for the degenerate high-ℓ Rydberg states. Multichannel quantum defect theory (MQDT) was used to analyze the millimeter wave data and to determine the hyperfine structures of the ^2P_{3/2} ground electronic states of ^{129}Xe^+ and ^{131}Xe^+.
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