Boron-nitrogen hydride (BNHx) materials are potentially important for hydrogen storage. The H(BH2NH2)nH oligomers might result from dehydrogenation of NH3BH3 and NH4BH4 materials. Understanding geometries, stabilities, and electronic structure of the resulting oligomers is essential for developing BNHx-based hydrogen storage materials. In this work we have performed computational modeling on the H(BH2NH2)nH (n = 1 ? 6) oligomers using density functional theory (DFT). Through Car-Parrinello molecular dynamics simulations and geometry optimizations, we have investigated the effects of coiling, branching, biradicalization, and cyclization on their stability. The reaction energetics and kinetic barriers for dihydrogen release were also investigated. It is shown that linear oligomers are unstable with respect to coiling and branching. We also show that the dehydrogenation step is exothermic, typically by less than 10 kcal/(mol of H2). The dihydrogen bonding, in which protic H(N) hydrogens are interacting with hydridic H(B) hydrogens, plays a vital role in stabilizing different structures or conformers of the reactants, transition states, and products.