The authors demonstrate that, for excited-core Rydberg states of high angular momentum
l, a simple relationship exists between the autoionization rate and the quantum defect of the corresponding ground-core state. For many cases, both quantities can be expressed in terms of the dipole polarizability of the core. The autoionization rates of the excited-core Sr (
5pnl) states are calculated as an example, and compared to existing experimental data.
This paper is devoted to the autoionization process of large-angular-momentum Rydberg states. After a brief account of autoionization formalism in nonrelativistic theory and single-configuration approximation, we apply it to atomic states with one electron of large angular momentum. The dominant contribution is the direct one and the exchange contribution is ignored. In this framework, the autoionization width varies with the principal quantum number as ${n}^{\mathrm{\ensuremath{-}}3}$ and exponentially with the angular momentum. When two excited electrons interact with a spherically symmetric core, it is demonstrated that the interaction between the Rydberg electron and the core polarized by the valence electron is proportional to the interaction between the two active electrons. Using newly derived radial matrix elements, we obtain a generally good agreement between our results and experiments on barium and strontium. Large-l Rydberg states are shown to be stable versus autoionization as soon as l is about 7. Possible refinements of our method are reviewed.
Calculations of the static electric-dipole scalar and tensor polarizabilities are presented for two alkali-metal atoms, Rb and Cs, for the $nS, n{P}_{\textonehalf{},\phantom{\rule{0.16em}{0ex}}3/2}$, and
nD3/2,5/2 states with large principal quantum numbers up to
n=50. The calculations are performed within an effective one-electron approximation, based on the Dirac-Fock Hamiltonian with a semiempirical core-polarization potential. The obtained results are compared with those from a simpler semiempirical approach and with available experimental data.
The dominant long-range interaction of an alkali-metal atom with charged particles at low energies is given for large separation R by the dispersive potential $W\ensuremath{\simeq}\ensuremath{-}{\ensuremath{\alpha}}_{d}{/R}^{4}$ in terms of the dipole polarizability ${\ensuremath{\alpha}}_{d}.$ For atoms prepared initially in Rydberg states of quantum numbers (n, l), the potential assumes a more complicated form due to the complete or near degeneracy of the n manifold. Contributions to the polarizability are treated in two parts, (a) one for the nondegenerate states and (b) the other for the degenerate or near degenerate cases. It is shown that ${\stackrel{\ifmmode \tilde{}\else \~{}\fi{}}{\ensuremath{\alpha}}}_{d}^{(b)}$ for case (b) is in general R dependent, and in the limit of complete degeneracy, diverges as
R2. That is, for a small energy gap \ensuremath{\Delta} between a pair of nearly degenerate states which are dipole coupled, the dispersion potential ${W}^{(b)}\ensuremath{\simeq}{D/R}^{2}$ for
R<Rx and ${W}^{(b)}\ensuremath{\simeq}\ensuremath{-}{\ensuremath{\alpha}}_{d}^{(b)}{/R}^{4}$ for
R>Rx, where D is the dipole moment, ${R}_{x}=[2|D/\ensuremath{\Delta}|{]}^{1/2},$ and ${\ensuremath{\alpha}}_{d}^{(b)}\ensuremath{\simeq}{D}^{2}/\ensuremath{\Delta}.$ They may also compete with a
1/R3 potential for Rydberg atoms with
l>0. The total ${\ensuremath{\alpha}}_{d}$ can be very large in magnitude for small \ensuremath{\Delta} and even assume negative values, but the corresponding
Rx also increases as \ensuremath{\Delta} decreases. The validity region in R of the ${R}^{\ensuremath{-}4}$ behavior of the potential recedes to larger R as the polarizability grows. A general formula for ${\ensuremath{\alpha}}_{d}$ is given, taking into account the effects of fine-structure splitting, the Lamb shift, and quantum defects.
The theory is developed for one- and two-atom interactions when the atom has a Rydberg electron attached to a hyperfine-split core state. This situation is relevant for some of the rare-earth and alkaline-earth atoms that have been proposed for experiments on Rydberg-Rydberg interactions. For the rare-earth atoms, the core electrons can have a very substantial total angular momentum
J and a nonzero nuclear spin
I. In the alkaline-earth atoms there is a single (
s) core electron whose spin can couple to a nonzero nuclear spin for odd isotopes. The resulting hyperfine splitting of the core state can lead to substantial mixing between the Rydberg series attached to different thresholds. Compared to the unperturbed Rydberg series of the alkali-metal atoms, the series perturbations and near degeneracies from the different parity states could lead to qualitatively different behavior for single-atom Rydberg properties (polarizability, Zeeman mixing and splitting, etc.) as well as Rydberg-Rydberg interactions (
C5 and
C6 matrices).