Relaxation experiments performed on alkali atoms polarized in their ground state by optical pumping in the presence of a rare gas have been previously reported and interpreted. It was shown that the relaxation governed by the spin-orbit interaction is strongly affected by the formation of chemically unstable Rb-Kr molecules bound by van der Waals forces. The previous theoretical analysis, restricted to the longitudinal relaxation, is extended here to relaxation processes involving the transverse components of the electronic polarization and hyperfine "coherences" (elements of the density matrix between different hyperfine states). The effects resulting from the action of a rf field are also examined. The main results of this work, among others, are (a) the prediction of a Zeeman transition-line pressure shift, in some circumstances larger by several orders of magnitude than the one calculated by Herman, and having a very peculiar variation with the rare-gas pressure; (b) a quantitative explanation of the anomalous pressure dependence of the hyperfine transition linewidth discovered by Bender and Cohen; (c) a proposal of a method of detection of rf transitions between states of the alkali---rare-gas molecules by their effect on the relaxation process.
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