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[arXiv: 2308.01336 and 2411.08737] We explore the impact of highly excited bound states on the evolution of number densities of new physics particles, specifically dark matter, in the early Universe. Focusing on dipole transitions within perturbative, unbroken gauge theories, we develop an efficient method for including around a million bound state formation and bound-to-bound transition processes. This enables us to examine partial-wave unitarity and accurately describe the freeze-out dynamics down to very low temperatures. We find that unitarity is systematically violated in perturbative leading order calculations below a critical velocity, even for arbitrarily small couplings given sufficiently highly excited states are regarded and initial states are less attractive than the captured bound states. In the non-Abelian case, we find that highly excited states can prevent the particles from freezing out, supporting a continuous depletion in the regime consistent with perturbativity and unitarity. We apply our formalism to a simplified dark matter model featuring a colored and electrically charged t-channel mediator. Our focus is on the regime of superWIMP production which is commonly characterized by a mediator freeze-out followed by its late decay into dark matter. In contrast, we find that excited states render mediator depletion efficient all the way until its decay, introducing a dependence of the dark matter density on the mediator lifetime as a novel feature. The impact of bound states on the viable dark matter mass can amount to an order of magnitude, relaxing constraints from Lyman-α observations.
