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@ARTICLE{Blanchard:13318,
author = {Blanchard, D. and Riktor, M. and Maronsson, J. and
Jacobsen, H. and Kehres, J. and Sveinbjörnsson, D. and
Bardaji, E. and Léon, A. and Juranyi, F. and Wuttke, J. and
Hauback, B. and Fichtner, M. and Vegge, T.},
title = {{H}ydrogen {R}otational and {T}ranslational {D}iffusion in
{C}alcium {B}orohydride from {Q}uasielastic {N}eutron
{S}cattering and {DFT} {C}alculations},
journal = {The journal of physical chemistry / C},
volume = {114},
issn = {1932-7447},
address = {Washington, DC},
publisher = {Soc.},
reportid = {PreJuSER-13318},
pages = {20249 - 20257},
year = {2010},
note = {This work is based on experiments performed at the Swiss
spallation neutron source SINQ, Paul Scherrer Institute,
Villigen, Switzerland and at FRMII, JCNS Garching, Germany.
The authors would like to acknowledge the European Graduate
School for Sustainable Energy Technology and the Nordic
Center for Excellence on Hydrogen Storage Materials. The
Danish Center for Scientific Computing is acknowledged for
super-computer access. The Center for Atomic Materials
Design (CAMD) is supported by the Lundbeck Fondation.
Financial support by EU-IP NESSHY (Contract #518271) and the
ERA-NET project Hy-CO is also gratefully acknowledged.},
abstract = {Hydrogen dynamics in crystalline calcium borohydride can be
initiated by long-range diffusion or localized motion such
as rotations, librations, and vibrations. Herein, the
rotational and translational diffusion were studied by
quasielastic neutron scattering (QENS) by using two
instruments with different time scales in combination with
density functional theory (DFT) calculations. Two thermally
activated reorientational motions were observed, mound the
2-fold (C-2) and 3-fold (C-3) axes of the BH4- units, at
temperature from 95 to 280K. The experimental energy
barriers (Ea(C2) = 0.14 eV and Ea(C3) = 0.10 eV) and mean
residence times are comparable with those obtained from DFT
calculations. Long-range diffusion events, with an energy
barrier Of E-aD = 0.12 eV and an effective jump length of
similar to 2.5 angstrom were observed at 224 and 260 K.
Three vacancy-mediated diffusion events, H jumps between two
neighboring BH4-, and diffusion of BH4- and BH3 groups were
calculated and finally discarded because of their very high
formation energies and diffusion barriers. Three
interstitial diffusion processes (H, H-2, and H2O) were also
calculated. The H interstitial was found to be highly
unstable, whereas the H-2 interstitial has a low energy of
formation (0.40 eV) and diffusion barrier (0.09 eV) with a
jump length (2.1 angstrom) that corresponds well with the
experimental values. H2O interstitial has an energy of
formation of -0.05 eV, and two different diffusion pathways
were found. The first gives a H jump distance of 2.45
angstrom with a diffusion barrier of 0.68 eV, the second
one, more favorable, exhibits a H jump distance of 1.08
angstrom with a barrier of 0.40 eV. The correlation between
the QENS and DFT calculations indicates that, most probably,
it is the diffusion of interstitial H-2 that was observed.
The origin of the interstitial H-2 might come from the
synthesis of the compound or a side reaction with trapped
synthesis residue leading to the partial oxidation of the
compound and hydrogen release.},
keywords = {J (WoSType)},
cin = {IFF-4 / Jülich Centre for Neutron Science JCNS (JCNS) ;
JCNS},
ddc = {540},
cid = {I:(DE-Juel1)VDB784 / I:(DE-Juel1)JCNS-20121112},
pnm = {Großgeräte für die Forschung mit Photonen, Neutronen und
Ionen (PNI) / BioSoft: Makromolekulare Systeme und
biologische Informationsverarbeitung},
pid = {G:(DE-Juel1)FUEK415 / G:(DE-Juel1)FUEK505},
experiment = {EXP:(DE-MLZ)SPHERES-20140101},
shelfmark = {Chemistry, Physical / Nanoscience $\&$ Nanotechnology /
Materials Science, Multidisciplinary},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000284455200051},
doi = {10.1021/jp107281v},
url = {https://juser.fz-juelich.de/record/13318},
}