The formation of meta-stable dark matter bound states in coannihilating scenarios could efficiently occur through the scattering with a variety of Standard Model bath particles, where light bosons during the electroweak cross over or even massless photons and gluons are exchanged in the t-channel. The amplitudes for those higher-order processes, however, are divergent in the collinear direction of the in- and out-going bath particles if the mediator is massless. To address the issue of collinear divergences, we derive the bound-state formation collision term in the framework of non-equilibrium quantum field theory. The main result is an expression for a more general cross section, which allows to compute higher-order bound-state formation processes inside the primordial plasma background in a comprehensive manner. Based on this result, we show that next-to-leading order contributions, including the bath-particle scattering, are i) collinear finite and ii) generically dominate over the on-shell emission for temperatures larger than the absolute value of the binding energy. Based on a simplified model, we demonstrate that the impact of these new effects on the thermal relic abundance is significant enough to make it worthwhile to study more realistic coannihilation scenarios.
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