Isomers and Conformers of H(NH₂BH₂)(n)H Oligomers: Understanding the Geometries and Electronic Structure of Boron-Nitrogen-Hydrogen Compounds as Potential Hydrogen Storage Materials
Boron-nitrogen-hydrogen (BNHx) materials are polar analogs of hydrocarbons with potential applications as media for hydrogen storage. As H(NH₂BH₂)nH oligomers result from dehydrogenation of NH₃BH₃ and NH₄BH₄ materials, understanding the geometries, stabilities, and electronic structure of these oligomers is essential for developing chemical methods of hydrogen release and regeneration of the BNHx-based hydrogen storage materials. In this work we have performed computational modeling on the H(NH₂BH₂)nH (n = 1 – 6) oligomers using density functional theory (DFT). We have investigated linear chain structures and the stabilizing effects of coiling, biradicalization, and branching through Car-Parrinello molecular dynamics simulations and geometry optimizations. We find that the zig-zag linear oligomers are unstable with respect to the coiled, square-wave chain, and branched structures, with the coiled structures being the most stable. Dihydrogen bonding in oligomers, where protic Hδ⁺(N) hydrogens interact with hydridic Hδ⁻(B) hydrogens, plays a crucial role in stabilizing different isomers and conformers. The results are consistent with structures of products that are seen in experimental NMR studies of dehydrogenated ammonia borane.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 902670
- Report Number(s):
- PNNL-SA-51976; 9601; KP1704020; TRN: US200717%%606
- Journal Information:
- Journal of Physical Chemistry C, 111(8):3294-3299, Vol. 111, Issue 8
- Country of Publication:
- United States
- Language:
- English
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