High-level electronic structure calculations have been used to map out the relevant portions of the potential energy surfaces for the release of H-2 from dimers of ammonia borane, BH3NH3 (AB). Using the correlation-consistent aug-cc-pVTZ basis set at the second-order perturbation MP2 level, geometries of stationary points were optimized. Relative energies were computed at these points using coupled-cluster CCSD(T) theory with the correlation-consistent basis sets at least up to the aug-cc-pVTZ level and in some cases extrapolated to the complete basis set limit. The results show that there are a number of possible dimers involving different types of hydrogen-bonded interactions. The most stable gaseous phase (AB)(2) dimer results from a head-to-tail cyclic conformation and is stabilized by 14.0 kcal/mol with respect to two AB monomers. (AB)(2) can generate one or two H-2 molecules via several direct pathways with energy barriers ranging from 44 to 50 kcal/mol. The diammoniate of diborane ion pair isomer, [BH4-][NH3BH2NH3+] (DADB), is 10.6 kcal/mol less stable than (AB)(2) and can be formed from two AB monomers by overcoming an energy barrier of similar to 26 kcal/mol. DADB can also be generated from successive additions of two NH3 molecules to B2H6 and from condensation of AB with separated BH3 and NH3 Molecules. The pathway for H-2 elimination from DADB is characterized by a smaller energy barrier of 20.1 kcal/mol. The alternative ion pair [NH4+][BH3NH2BH3-] is calculated to be 16.4 kcal/mol above (AB)(2) and undergoes H-2 release with an energy barrier of 17.7 kcal/mol. H-2 elimination from both ion pair isomers yields the chain BH3NH2BH,NH3 as product. Our results suggest that the neutral dimer will play a minor role in the release of H-2 from ammonia borane, with a dominant role from the ion pairs as observed experimentally in ionic liquids and the solid state.