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Physical Review A

Stark-effect studies in xenon autoionizing Rydberg states using a tunable extreme-ultraviolet laser source

Wolfgang Ernst, T. P. Softley, Richard N. Zare

Published Jun 1, 1988• 78 citations
Publisher

Abstract

The Stark spectra of autoionizing Rydberg states of Xe converging to the second ionization limit 5${p}^{5}$ $^{2}P_{1/2}$ have been investigated as a function of applied electric field over the range 26--2362 V/cm. Single-photon excitation from the Xe ground state was achieved using coherent radiation near 92.5 nm, generated by frequency tripling the pulsed output of a frequency-doubled dye laser in a free jet of rare-gas atoms. For the lowest electric field only the ns' and nd' series were observed. As the electric field was increased the np' series appeared because of the mixing of wave functions with different l values. Further increase of the electric field caused the appearance of hydrogenlike Stark manifolds. The Stark spectrum was simulated in a two-step procedure with no adjustable parameters. Using a jl-coupling basis set the Hamiltonian matrix was diagonalized to determine the energy levels and corresponding eigenfunctions for a given electric field strength. The intensities and line shapes were then calculated using the formalism developed by Fano for a many-discrete-level--single-continuum configuration interaction. This treatment was sufficient to reproduce the positions, widths, and shapes of most observed features. At field strengths between 1000 and 2000 V/cm, however, an additional modulation structure with a spacing of about 2.7 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$ appeared on top of the \ensuremath{\Vert}M\ensuremath{\Vert}=1 autoionizing resonances, which could not be explained by our simple theoretical model.

DOI
10.1103/physreva.37.4172

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The Stark spectra of autoionizing Rydberg states of Xe converging to the second ionization limit 5p5{p}^{5}p5 2P1/2^{2}P_{1/2}2P1/2​ have been investigated as a function of applied electric field over the range 26--2362 V/cm. Single-photon excitation from the Xe ground state was achieved using coherent radiation near 92.5 nm, generated by frequency tripling the pulsed output of a frequency-doubled dye laser in a free jet of rare-gas atoms. For the lowest electric field only the ns' and nd' series were observed. As the electric field was increased the np' series appeared because of the mixing of wave functions with different l values. Further increase of the electric field caused the appearance of hydrogenlike Stark manifolds. The Stark spectrum was simulated in a two-step procedure with no adjustable parameters. Using a jl-coupling basis set the Hamiltonian matrix was diagonalized to determine the energy levels and corresponding eigenfunctions for a given electric field strength. The intensities and line shapes were then calculated using the formalism developed by Fano for a many-discrete-level--single-continuum configuration interaction. This treatment was sufficient to reproduce the positions, widths, and shapes of most observed features. At field strengths between 1000 and 2000 V/cm, however, an additional modulation structure with a spacing of about 2.7 cm\ensuremath−1{\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}cm\ensuremath−1 appeared on top of the \ensuremath{\Vert}M\ensuremath{\Vert}=1 autoionizing resonances, which could not be explained by our simple theoretical model.
The first detailed observation of the perturbations by an electric field of the Rydberg autoionizing resonances of a rare-gas atom is reported. The Stark spectroscopy of autoionizing Rydberg states converging to the second ionization limit $4{p}^{5}^{2}P_{\frac{1}{2}}^{o}$ in Kr I is performed in an atomic beam with the use of a two-step laser excitation from the 4p55s[32]204{p}^{5}5s{[\frac{3}{2}]}_{2}^{0}4p55s[23​]20​ metastable state. In addition to the verification of the ${({n}^{*})}^{\ensuremath{-}3}$ dependence of the zero-field width of two autoionizing series and of the linear dependence of the Stark-manifold splittings with the electric field, we have observed an (n)0.7{(n)}^{0.7}(n)0.7 law for the dependence of the Stark-manifold splitting along the series, an important narrowing and dissymmetrization of the $n{d}^{\ensuremath{'}}$ resonances, and a nonlinear-field behavior of Stark-manifold components in the vicinity of the first anticrossing. Discussions are carried out with the use of the recent work on Rydberg-Stark spectroscopy and on autoionizing states in two-electron atoms.
We have studied the Stark effect for the bound Rydberg states of xenon (2{(}^{2}(2P3/2{\mathrm{P}}_{3/2}P3/2​ core) in the vicinity of n=17. These are the first detailed measurements of Rydberg-state Stark structure in a heavy rare-gas atom. The experiment was performed by one-photon laser spectroscopy from the metastable 6s'[(1/2)]0{[(1/2)]}_{0}[(1/2)]0​ state in an atomic beam. Laser polarization can be chosen to excite pure M=0 or \ensuremath{\Vert}M\ensuremath{\Vert}=1 levels. Stark maps are presented for electric fields from 0 to 2000 V/cm. The major low-field features are a prominent linear manifold for states with l\ensuremath{\ge}3 and an isolated group of states arising from mixing within the overlapping p and d terms. A simple model of the p,d complex, showing strong mixing at fields as low as 200 V/cm, is used to correlate observed states with the zero-field states. The spectra become exceedingly complex for fields greater than 1000 V/cm because of mixing within the extensive fine structure of xenon.
We have studied experimentally and theoretically two-step photoionization through the 3P state of sodium in an electric field of up to 3.90 kV/cm. The apparatus uses an atomic beam crossed by two pulsed laser beams, one at 589 nm for the first step, and the other swept through the zero field threshold Eo near 409 nm for the ionization. We observe broad undulations in the photocurrent above Eo that narrow with decreasing energy and eventually sharpen into well-defined but asymmetric transitions to Stark-shifted Rydberg states. We calculate the oscillator strength density for the appropriate transitions using modified hydrogenic wave functions and find excellent agreement for the position and relative strength of all the spectral features. We model the asymmetries as Fano-type interferences between quasi-discrete and continuum ionization channels. Using appropriate core potentials, and taking into account core-induced coupling of both discrete-to-continuum and continuum-to-continuum states, we obtain estimates of Fano's q and Ɖ that agree reasonably well with our measurements.
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The nonresonant, three-photon ionization spectrum of atomic Xe in the region between the Xe+{\mathrm{Xe}}^{+}Xe+ 23/2^{2}\mathrm{}_{3/2}23/2​ and 21/2^{2}\mathrm{}_{1/2}21/2​ fine-structure limits is reported. Using linearly polarized light, four autoionizing Rydberg series are observed converging to the Xe+{\mathrm{Xe}}^{+}Xe+ 21/2^{2}\mathrm{}_{1/2}21/2​ limit, corresponding to (2{(}^{2}(2P\ifmmode^\circ\else\textdegree\fi{}1/2{\mathrm{}}_{1/2}1/2​)ns'[(1/2)]\ifmmode^\circ\else\textdegree\fi{}1{\mathrm{}}_{1}1​, (2P\ifmmode^\circ\else\textdegree\fi{}1/2{\mathrm{}}_{1/2}1/2​)nd'[(3/2)]\ifmmode^\circ\else\textdegree\fi{}1{\mathrm{}}_{1}1​, (2{(}^{2}(2P\ifmmode^\circ\else\textdegree\fi{}1/2{\mathrm{}}_{1/2}1/2​)nd'[(5/2)]\ifmmode^\circ\else\textdegree\fi{}3{\mathrm{}}_{3}3​, and (2{(}^{2}(2P\ifmmode^\circ\else\textdegree\fi{}1/2{\mathrm{}}_{1/2}1/2​)ng'[(7/2)]\ifmmode^\circ\else\textdegree\fi{}3{\mathrm{}}_{3}3​; as expected, using circularly polarized light only the J=3 series are observed. These results are in contrast to earlier experimental work in which no resonant structure was observed. Photoelectron angular distributions are reported for the (2{(}^{2}(2P\ifmmode^\circ\else\textdegree\fi{}1/2{\mathrm{}}_{1/2}1/2​)9s'[(1/2)]\ifmmode^\circ\else\textdegree\fi{}1{\mathrm{}}_{1}1​ and the (2{(}^{2}(2P\ifmmode^\circ\else\textdegree\fi{}1/2{\mathrm{}}_{1/2}1/2​)7d'[(3/2)]\ifmmode^\circ\else\textdegree\fi{}3{\mathrm{}}_{3}3​ autoionizing resonances. The results are compared with the recent theoretical calculations by P. Gangopadhyay et al. [Phys. Rev. A 34, 2998 (1986)].