The collisional angular-momentum mixing of $n=5\ensuremath{-}15$ Na
d states with the
l>2 states of the same
n has been studied using He, Ne, and Ar as collision partners. At rare-gas pressures of \ensuremath{\sim}1 Torr, the $l\ensuremath{\ge}2$ states are thoroughly mixed and the mixture decays at the average radiative lifetime of all the $l\ensuremath{\ge}2$ states of the same
n. Using \ensuremath{\sim}1 Torr of neon to collisionally mix the $l\ensuremath{\ge}2$ states, the average lifetime for $l\ensuremath{\ge}2$ was measured for each
n and compared to the theoretical prediction for hydrogen, with which it is in excellent agreement. The cross section for
l mixing by each of the gases is found to increase sharply from
n=5to10 and decrease above
n=10. The magnitudes of the
l-mixing cross sections are found to correlate with the low-energy scattering lengths of the collision partners.
Ion formation in sodium vapor (\ensuremath{\sim}
1011 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}3}$) containing Rydberg atoms (18\ensuremath{\le}n\ensuremath{\le}35) was investigated. Both atomic ions and diatomic molecular ions resulting from collisions between highly excited sodium,
Na∗∗, and Na(3s) were observed. However, the predominant production mechanism was found to be photoionization of
Na∗∗ by blackbody radiation, the rate of which was measured at 500 K and found to be \ensuremath{\simeq}5.7\ifmmode\times\else\texttimes\fi{}
103 ${\mathrm{sec}}^{\mathrm{\ensuremath{-}}1}$ for n=18, in good agreement with theory. The
Na+ signal from blackbody photoionization is observed to be independent of n, which we interpret as implying rapid and nearly complete self-l-mixing, mixing by collisions with Na(3s) atoms, for both s and d states. It is probable, however, that the s states are mixed to the adjacent, n-1, manifold of l states. It was also found that the heavy-body collision cross sections for
Na+ and
Na2+ formation, while roughly three orders of magnitude lower than our estimate of the self-l-mixing cross section, are appreciable, of order 100 A
˚2.
The collisional angular-momentum mixing of the
Nand Rydberg states into states of higher angular momentum with Xe as the collisional partner has been studied in zero field and in the presence of a small electric field. The collisional
l-mixing cross section in zero field has been measured for $9\ensuremath{\le}n\ensuremath{\le}23$ using a vapor-cell-fluorescence method and a crossed-beam technique with a selective-field-ionization (SFI) scheme as the state detector. Using the
∣ml∣ selectivity of the SFI, we have also investigated the final-
∣ml∣-state distribution of the collisionally populated states of
l>2. Our measurements suggest that the collisionally populated states have predominantly low
∣ml∣ values ($|{m}_{l}|\ensuremath{\le}2$). An application of a low electric field (\ensuremath{\sim} 50 V/cm) substantially reduces the collisional population of the low-
∣ml∣ states, thus reducing the total cross section as well.
A classical model for l mixing of Rydberg states in atomic collisions is described. The primary assumption of the model is that l changing occurs in a single hard-sphere collision between the Rydberg electron and the perturbing atom which is represented by the zero-energy scattering length L. Predictions of the model, which are in the form of cross sections as functions of principal quantum number n, are compared with data for l mixing of Na(nd) and Rb(nf) by rare-gas atoms. Agreement is, in most cases, quite good, comparable with that of other, more sophisticated, models. It is shown that, because the calculation must be carried out in the reference frame of the ion core, the energy deficit between low angular momentum states and the nearest hydrogenic manifold can be made up in a single collision between the Rydberg electron and the perturbing atom, an effect that is analogous to the gravitational slingshot effect used to alter the orbits of a spacecraft under the influence of the Sun's gravitational field. Comparison of data for l mixing by ground-state Rb atoms with model calculations in which L is treated as a free parameter leads to an estimate of 10 a.u. for the zero-energy scattering length of Rb.
For $20\ensuremath{\le}n\ensuremath{\le}45$, two types of quasielastic state-changing-collisional (QESCC) processes, i.e., (i)
l-changing and (ii)
n-and
l-changing processes, have been theoretically investigated based on the free-electron model in which an excited Rydberg electron behaves as if it were "free" and slow with its interaction with a rare-gas atom playing a decisive role. It is shown that a parameter ${u}_{min}[=\frac{\ensuremath{\nu}{\ensuremath{\nu}}^{\ensuremath{'}}\ensuremath{\Delta}E{a}_{0}}{(\ensuremath{\hbar}V)}]$ is quite useful for characterizing both of these QESCC processes in a unified way where $\ensuremath{\nu}(\ensuremath{\simeq}{\ensuremath{\nu}}^{\ensuremath{'}})$ is an effective principal quantum number of the initial (final) state, $\ensuremath{\Delta}E$ is an energy defect, and
V is a relative velocity. It is theoretically found that higher-angular-momentum states are dominantly populated in the final channel of these QESCC processes with $1<{u}_{min}\ensuremath{\lesssim}\ensuremath{\nu}$ such as in the
n- and
l-changing collision of
Rb∗∗(ns)+He. This is in contrast with the uniform distribution over the final angular-momentum states for the usual
l-changing processes, i.e., ${u}_{min}\ensuremath{\lesssim}1$. The calculated cross sections of these QESCC processes with $1<{u}_{min}\ensuremath{\lesssim}\ensuremath{\nu}$ are found to be in reasonable agreement with experimental findings available at present.