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Autori principali: Nagle-Cocco, Liam A. V., Schneemann, Andreas, Stone, Kevin H., Stavila, Vitalie, Gennett, Thomas, Strange, Nicholas A.
Natura: Preprint
Pubblicazione: 2025
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Accesso online:https://arxiv.org/abs/2508.03874
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author Nagle-Cocco, Liam A. V.
Schneemann, Andreas
Stone, Kevin H.
Stavila, Vitalie
Gennett, Thomas
Strange, Nicholas A.
author_facet Nagle-Cocco, Liam A. V.
Schneemann, Andreas
Stone, Kevin H.
Stavila, Vitalie
Gennett, Thomas
Strange, Nicholas A.
contents Hexammine magnesium borohydride, Mg(NH$_3$)$_6$(BH$_4$)$_2$, consists of adducted NH$_3$ molecules locked in a matrix of Mg cations and borohydride anions. It is a candidate material for hydrogen storage, with 16.8wt\% hydrogen stored in both the NH$_3$ and borohydride anions. It also may be of interest as a Mg$^{2+}$ conducting electrolyte in solid state batteries. Its crystal structure has, until now, eluded a proper structural solution due to ambiguity regarding the NH$_3$ position and behaviour. In this work, we show using synchrotron X-ray diffraction that the room-temperature structure can be solved only with a model assuming orientational disorder of ammonia molecules within the crystal structure. Cooling the sample to 120\,K yields additional Bragg peaks, which can only be solved with a unit cell expansion consistent with a freezing of the orientational freedom of ammonia molecules. Using this insight from the structure solution, we perform a full assignment of the vibrational modes in the room-temperature IR spectrum.
format Preprint
id arxiv_https___arxiv_org_abs_2508_03874
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Orientational Disorder of NH$_3$ in Hexammine Magnesium Borohydride
Nagle-Cocco, Liam A. V.
Schneemann, Andreas
Stone, Kevin H.
Stavila, Vitalie
Gennett, Thomas
Strange, Nicholas A.
Materials Science
Chemical Physics
Hexammine magnesium borohydride, Mg(NH$_3$)$_6$(BH$_4$)$_2$, consists of adducted NH$_3$ molecules locked in a matrix of Mg cations and borohydride anions. It is a candidate material for hydrogen storage, with 16.8wt\% hydrogen stored in both the NH$_3$ and borohydride anions. It also may be of interest as a Mg$^{2+}$ conducting electrolyte in solid state batteries. Its crystal structure has, until now, eluded a proper structural solution due to ambiguity regarding the NH$_3$ position and behaviour. In this work, we show using synchrotron X-ray diffraction that the room-temperature structure can be solved only with a model assuming orientational disorder of ammonia molecules within the crystal structure. Cooling the sample to 120\,K yields additional Bragg peaks, which can only be solved with a unit cell expansion consistent with a freezing of the orientational freedom of ammonia molecules. Using this insight from the structure solution, we perform a full assignment of the vibrational modes in the room-temperature IR spectrum.
title Orientational Disorder of NH$_3$ in Hexammine Magnesium Borohydride
topic Materials Science
Chemical Physics
url https://arxiv.org/abs/2508.03874