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@ARTICLE{Blanchard:19977,
author = {Blanchard, D. and Maronsson, J.B. and Riktor, M.D. and
Kheres, J. and Sveinbjörnsson, D. and Bardají, E.G. and
Léon, A. and Juranyi, F. and Wuttke, J. and Lefmann, K. and
Hauback, B.C. and Fichtner, M. and Vegge, T.},
title = {{H}indered {R}otational {E}nergy {B}arriers of {BH}4-
{T}etrahedra in ß-{M}g ({BH}4)2 from {Q}uasielastic
{N}eutron {S}cattering and {DFT} {C}alculations},
journal = {The journal of physical chemistry / C},
volume = {116},
issn = {1932-7447},
address = {Washington, DC},
publisher = {Soc.},
reportid = {PreJuSER-19977},
pages = {2013 - 2023},
year = {2012},
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.
It has been supported by the Danish Council for independent
Research through DANSCATT. The authors 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 supercomputer 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 = {In this work, hindered rotations of the BH4- tetrahedra in
Mg(BH4)(2) were studied by quasielastic neutron scattering,
using two instruments with different energy resolution, in
combination with density functional theory (DFT)
calculations. Two thermally activated reorientations of the
BH4- units, around the 2-fold (C-2) and 3-fold (C-3) axes
were observed at temperatures from 120 to 440 K. The
experimentally obtained activation energies (E-aC2 = 39 and
76 meV and E-aC3 = 214 meV) and mean residence times between
reorientational jumps are comparable with the energy
barriers obtained from DFT calculations. A linear dependency
of the energy barriers for rotations around the C-2 axis
parallel to the Mg-Mg axis with the distance between these
two axes was revealed by the DFT calculations. At the lowest
temperature (120 K) only $15\%$ of the BH4- units undergo
rotational motion and from comparison with DFT results it is
expectedly the BH4- units with the boron atom closest to the
Mg-Mg axis, although dynamics related to local disorder
existing at the boundary of the antiphase domains or to the
presence of solvent in the sample cannot be strictly
excluded. No long-range diffusion events were observed.},
keywords = {J (WoSType)},
cin = {ICS-1 / JCNS (München) ; Jülich Centre for Neutron
Science JCNS (München) ; JCNS-FRM-II / JCNS-1},
ddc = {540},
cid = {I:(DE-Juel1)ICS-1-20110106 /
I:(DE-Juel1)JCNS-FRM-II-20110218 /
I:(DE-Juel1)JCNS-1-20110106},
pnm = {BioSoft: Makromolekulare Systeme und biologische
Informationsverarbeitung / Großgeräte für die Forschung
mit Photonen, Neutronen und Ionen (PNI)},
pid = {G:(DE-Juel1)FUEK505 / G:(DE-Juel1)FUEK415},
experiment = {EXP:(DE-MLZ)SPHERES-20140101},
shelfmark = {Chemistry, Physical / Nanoscience $\&$ Nanotechnology /
Materials Science, Multidisciplinary},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000299584800045},
doi = {10.1021/jp208670v},
url = {https://juser.fz-juelich.de/record/19977},
}