An ab initio computational study of the reaction pathways for methanol-formaldehyde complexation is presented. This study serves as a prototype for novel dihydrogen exchange between the alcohol and ketone structures, such that the reactants and products are mirror images. The donated hydrogen atoms, both from the alcohol, are the hydroxyl group hydrogen and one of the carbon hydrogen atoms. Whereas the motion of the former hydrogen atom is known to be facile, as facilitated by formation of a hydrogen bond, the barrier to the latter hydrogen atom transfer was not known. In the present work, the barrier for the dihydrogen transfer is determined to be 33.1 kcal/mol, with the reaction proceeding via a hexagonal transition state structure. By contrast, the second excited singlet state is characterized by a potential well at the geometry corresponding to that of the transition state on the ground state surface and manifests the facile donation of both hydrogen atoms. The presence of a sufficiently high ground state surface barrier, coupled with an excited state potential well, is a prerequisite for the coherently controlled interconversion of a chiral alcohol to the analogous ketone and that of the ketone to a chiral alcohol of the opposite handedness. Dihydrogen exchange reactions of this type could, therefore, serve as prototypes for coherently controlled racemic purification.