The alignment and the orientation of the electron charge cloud of the Li(2 2P), Na(3 2P)-state excited in 2.6 keV Li +, Na +-inert gas collisions is studied with the quasi-coincidence technique of Wittmann and Andrä. A polarization analysis of the photons emitted in the subsequent ( 2 P → 2 S) transitions has been carried out. The present experiment breaks rotational symmetry with respect to the primary beam direction, but possesses no full planar symmetry. Thus a direct experimental derivation of amplitudes for the capture process is not feasible. For Li + −He the characteristics of the quasi-coincidence technique could be studied in detail because experimental data obtained with the photon-scattered atom coincidence technique and theoretical studies are available. The results for Li + −He are consistent with the available results which showed that the well established 2pσ-2pπ rotational coupling is responsible for the first step in the capture process. The results support the prediction of the theory that the linear polarization P 2 changes its sign between 2.0 and 6.0 keV. The results for Li-Ar and Kr suggest that rotational coupling at small internuclear distances (similarly as for LiHe) is the dominant mechanism for capture with alkali atom excitation.