Cosmological hydrogen recombination: populations of the high level   sub-states
  We present results for the spectral distortions of the Cosmic Microwave Background (CMB) arising due to bound-bound transitions during the epoch of cosmological hydrogen recombination at frequencies down to nu~100MHz. We extend our previous treatment of the recombination problem now including the main collisional processes and following the evolution of all the hydrogen angular momentum sub-states for up to 100 shells. We show that, due to the low baryon density of the Universe, even within the highest considered shell full statistical equilibrium (SE) is not reached and that at low frequencies the recombination spectrum is significantly different when assuming full SE for n>2. We also directly compare our results for the ionization history to the output of the Recfast code, showing that especially at low redshifts rather big differences arise. In the vicinity of the Thomson visibility function the electron fraction differs by roughly -0.6% which affects the temperature and polarization power spectra by <~1%. Furthermore we shortly discuss the influence of free-free absorption and line broadening due to electron scattering on the bound-bound recombination spectrum and the generation of CMB angular fluctuations due to scattering of photons within the high shells. 
J. Chluba, J.A. Rubino-Martin and R.A. Sunyaev