Computational modeling of H(BH2NH2)nH oligomers

Understanding the electronic structures of boron-nitrogen hydrides as potential hydrogen storage materials

Jun Li, Shawn M. Kathmann, Gregory K. Schenter, John Linehan, Tom Autrey, Maciej Gutowski

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Abstract

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.

Original languageEnglish
Title of host publicationACS National Meeting Book of Abstracts
Volume232
Publication statusPublished - 2006
Event232nd American Chemical Society Meeting and Exposition - San Francisco, CA, United States
Duration: Sep 10 2006Sep 14 2006

Other

Other232nd American Chemical Society Meeting and Exposition
CountryUnited States
CitySan Francisco, CA
Period9/10/069/14/06

Fingerprint

Boron
Hydrogen storage
Oligomers
Hydrides
Electronic structure
Nitrogen
Dehydrogenation
Hydrogen
Geometry
Cyclization
Density functional theory
Molecular dynamics
Railroad cars
Kinetics
Computer simulation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Li, J., Kathmann, S. M., Schenter, G. K., Linehan, J., Autrey, T., & Gutowski, M. (2006). Computational modeling of H(BH2NH2)nH oligomers: Understanding the electronic structures of boron-nitrogen hydrides as potential hydrogen storage materials. In ACS National Meeting Book of Abstracts (Vol. 232)

Computational modeling of H(BH2NH2)nH oligomers : Understanding the electronic structures of boron-nitrogen hydrides as potential hydrogen storage materials. / Li, Jun; Kathmann, Shawn M.; Schenter, Gregory K.; Linehan, John; Autrey, Tom; Gutowski, Maciej.

ACS National Meeting Book of Abstracts. Vol. 232 2006.

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Li, J, Kathmann, SM, Schenter, GK, Linehan, J, Autrey, T & Gutowski, M 2006, Computational modeling of H(BH2NH2)nH oligomers: Understanding the electronic structures of boron-nitrogen hydrides as potential hydrogen storage materials. in ACS National Meeting Book of Abstracts. vol. 232, 232nd American Chemical Society Meeting and Exposition, San Francisco, CA, United States, 9/10/06.
Li J, Kathmann SM, Schenter GK, Linehan J, Autrey T, Gutowski M. Computational modeling of H(BH2NH2)nH oligomers: Understanding the electronic structures of boron-nitrogen hydrides as potential hydrogen storage materials. In ACS National Meeting Book of Abstracts. Vol. 232. 2006
Li, Jun ; Kathmann, Shawn M. ; Schenter, Gregory K. ; Linehan, John ; Autrey, Tom ; Gutowski, Maciej. / Computational modeling of H(BH2NH2)nH oligomers : Understanding the electronic structures of boron-nitrogen hydrides as potential hydrogen storage materials. ACS National Meeting Book of Abstracts. Vol. 232 2006.
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