The results of an experiment on the associative ionization collision between sodium and cesium excited atoms are reported. The atoms are excited by two resonant cw lasers to the 3
P3/2 and 6
P3/2 levels, respectively, and the formation of the
NaCs+ molecular ion is observed. The rate constant of such process has been measured relative to the known rate constant of sodium associative ionization and its value resulted in K=(5.4\ifmmode\pm\else\textpm\fi{}3.2)\ifmmode\times\else\texttimes\fi{}${10}^{\mathrm{\ensuremath{-}}11}$
cm3 ${\mathrm{s}}^{\mathrm{\ensuremath{-}}1}$.
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.