The molecular dynamics of the chemiluminescent reaction of Xe(3 P 2,0) with Br2, ICl, CH3I, CF3I and CCl4 have been studied at collision energies in the range 10–125 kJ mol-1 using a rotor accelerated cross-beam system. Individual measurements include chemiluminescence spectra of the rare gas halide products, their excitation functions and the translational energy dependence of their rotational alignment (obtained from the observed fluorescence polarization). The results correlate closely with the behaviour of the analogous alkali metal atomic reactions despite the opportunity for curve crossings associated with the multiplicity of electronically excited potential surfaces. Simple dynamical models (e.g. the DIPR model) are used to assess the relative importance of kinematic and dynamical factors, particularly in controlling the degree of alignment impressed on the rotating rare gas halide product.