Calculations of electron momentum distributions for equilibrium geometries, employing advanced Dyson orbital theories and statistical thermodynamics beyond the RRHO approximation, fail to quantitatively reproduce the outermost momentum distribution profile inferred from (e, 2e) electron impact ionization experiments on ethanol employing high-resolution electron momentum spectroscopy. A very detailed study of the influence on this momentum distribution of nuclear dynamics in the initial ground state and in the final ionized state is presented according to a thermal averaging over exceedingly large sets of model structures as well as Born-Oppenheimer molecular dynamical simulations on the potential energy surface of the radical cation. Our results give very convincing albeit qualitative indications that the strong turn-up of the (e, 2e) ionization intensities characterizing the highest occupied molecular orbital (HOMO) of ethanol at low electron momenta is the combined result of (1) the extraordinarily flat nature of the conformational energy map of ethanol, which enables significant departures from energy minima in the ground electronic state, (2) strong anomeric interactions between an oxygen lone pair and the central C-C bond for the minor but significant fraction of conformers exhibiting a hydroxyl torsion angle (alpha) at around 90 degrees, and, last but not least, (3) the possibility to observe with this minor conformer fraction ultrafast and highly significant extensions of the central C-C bond, resulting, in turn, in an enhanced delocalization of the HOMO from the oxygen lone pair region onto the methyl group, immediately after the sudden removal of an electron. This charge transfer appears to occur at the very first stages, that is, within an effective time scale on the order of approximately 10 fs, of an ultrafast dissociation of the ethanol radical cation into a methyl radical and a protonated form of formaldehyde.