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Title: Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations

Abstract

We investigated the structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (α, β, γ, and δ phases) with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4- anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20–80 meV) are associated with the BH4- librational modes. The features in the intermediate energy region (80–120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120–200 meV) correspond to the BH4- symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. We can explain these differences using the spatial distribution of BH4- anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. Our results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.

Authors:
 [1];  [2];  [3];  [2];  [2];  [3]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). NIST Center for Neutron Research
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). NIST Center for Neutron Research
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1338381
Report Number(s):
SAND2016-12365J
Journal ID: ISSN 1463-9076; PPCPFQ; 649735; TRN: US1701710
Grant/Contract Number:  
AC04-94AL85000; AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 18; Journal Issue: 36; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Dimitrievska, Mirjana, White, James L., Zhou, Wei, Stavila, Vitalie, Klebanoff, Leonard E., and Udovic, Terrence J. Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations. United States: N. p., 2016. Web. doi:10.1039/C6CP04469G.
Dimitrievska, Mirjana, White, James L., Zhou, Wei, Stavila, Vitalie, Klebanoff, Leonard E., & Udovic, Terrence J. Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations. United States. doi:10.1039/C6CP04469G.
Dimitrievska, Mirjana, White, James L., Zhou, Wei, Stavila, Vitalie, Klebanoff, Leonard E., and Udovic, Terrence J. Fri . "Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations". United States. doi:10.1039/C6CP04469G. https://www.osti.gov/servlets/purl/1338381.
@article{osti_1338381,
title = {Structure-dependent vibrational dynamics of Mg(BH 4 ) 2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations},
author = {Dimitrievska, Mirjana and White, James L. and Zhou, Wei and Stavila, Vitalie and Klebanoff, Leonard E. and Udovic, Terrence J.},
abstractNote = {We investigated the structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (α, β, γ, and δ phases) with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4- anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20–80 meV) are associated with the BH4- librational modes. The features in the intermediate energy region (80–120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120–200 meV) correspond to the BH4- symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. We can explain these differences using the spatial distribution of BH4- anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. Our results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.},
doi = {10.1039/C6CP04469G},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 36,
volume = 18,
place = {United States},
year = {2016},
month = {8}
}

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