TY - JOUR
T1 - Mapping the complete bonding network in KBH4 using the combined power of powder diffraction and maximum entropy method
AU - Bindzus, Niels
AU - Cargnoni, Fausto
AU - Gatti, Carlo
AU - Richter, Bo
AU - Jensen, Torben R.
AU - Takata, Masaki
AU - Iversen, Bo B.
N1 - Funding Information:
We thank the Danish National Research Foundation (Center for Materials Crystallography, DNRF93) and the Danish Research Council for Nature and Universe (Danscatt) for funding this work. The RIKEN-Harima Institute is gratefully acknowledged for beam time at BL02B2 at the SPring-8 synchrotron facility.
Publisher Copyright:
© 2014 Elsevier B.V.
PY - 2015/2/1
Y1 - 2015/2/1
N2 - The combined power of the maximum entropy method (MEM) and synchrotron powder X-ray diffraction (SPXRD) is exerted to accurately reconstruct the electron density distribution (EDD) of the hydrogen storage material, KBH4. Its crystal structure features thermally activated disorder among the BH4- moieties, and weak secondary bonding effects occupy a key role in determining the energetic barrier for this dynamical effect. The MEM reconstruction is meticulously optimised and inspected for errors, in what may be envisaged as a general manual for this kind of studies. The successful outcome constitutes an experimental EDD of cutting-edge quality, from which atomic charges and the complete bonding network are mapped by topological descriptors. Remarkably, the chemical insights even extend to the delicate interplay of closed-shell bonding in excellent correspondence with ab initio and two-channel MEM calculations. For the current class of functional materials, access to such subtle electronic features is essential for the fundamental understanding of hydrogen desorption pathways.
AB - The combined power of the maximum entropy method (MEM) and synchrotron powder X-ray diffraction (SPXRD) is exerted to accurately reconstruct the electron density distribution (EDD) of the hydrogen storage material, KBH4. Its crystal structure features thermally activated disorder among the BH4- moieties, and weak secondary bonding effects occupy a key role in determining the energetic barrier for this dynamical effect. The MEM reconstruction is meticulously optimised and inspected for errors, in what may be envisaged as a general manual for this kind of studies. The successful outcome constitutes an experimental EDD of cutting-edge quality, from which atomic charges and the complete bonding network are mapped by topological descriptors. Remarkably, the chemical insights even extend to the delicate interplay of closed-shell bonding in excellent correspondence with ab initio and two-channel MEM calculations. For the current class of functional materials, access to such subtle electronic features is essential for the fundamental understanding of hydrogen desorption pathways.
KW - Electron density
KW - Hydrogen storage
KW - Maximum entropy method
KW - Synchrotron powder diffraction
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U2 - 10.1016/j.comptc.2014.09.014
DO - 10.1016/j.comptc.2014.09.014
M3 - Article
AN - SCOPUS:84920901867
VL - 1053
SP - 245
EP - 253
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
SN - 2210-271X
ER -