Gaseous lithium complex hydrides Li2MH5 (M = B, Al) have been studied using DFT/B3P86 and MP2 methods with 6-311++G(d,p) basis set. High content of hydrogen by these materials accord them with good candidacy as a class of hydrogen storage materials. The optimized geometrical parameters, vibrational spectra and thermodynamic properties of the hydrides and the subunits LiH, Li2H+, Li2H2, MH3, MH4−, and LiMH4 have been determined. For the LiBH4 the equilibrium configuration was tridentate of C3v symmetry. For LiAlH4 two isomeric forms, bidentate (C2v) and tridentate (C3v), were confirmed to exist, and C2v isomer was shown to dominate in saturated vapor. For complex hydrides Li2MH5, different structural forms were considered but only one asymmetric form (C1) appeared to be equilibrium. Several possible channels of dissociation of Li2MH5 were considered; the enthalpies and Gibbs free energies of the reactions were computed. The enthalpies of formation ∆fH(0) of the complex hydrides in gaseous phase were determined: 60 ± 10 kJmol1 (Li2BH5) and 33 ± 10 kJmol1 (Li2AlH5). Heterophase decomposition of the gaseous Li2MH5 with solid products LiH and B/Al and hydrogen gas release was shown to be spontaneous at ambient temperature. Production of hydrogen gas via gaseous decomposition is highly endothermic and achievable at elevated temperatures. The complexes Li2MH5 are therefore proposed to be useful hydrogen storage materials under appropriate conditions.
| Published in | International Journal of Computational and Theoretical Chemistry (Volume 3, Issue 6) |
| DOI | 10.11648/j.ijctc.20150306.13 |
| Page(s) | 58-67 |
| Creative Commons |
This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited. |
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Copyright © The Author(s), 2015. Published by Science Publishing Group |
Complex Hydrides, Hydrogen Storage, Geometrical Structure, Vibrational Spectra, Density Functional Theory, Møller–Plesset Perturbation Theory, Basis Set, Isomers, Thermodynamic Properties
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APA Style
Melkizedeck Hiiti Tsere, Tatiana P. Pogrebnaya, Alexander M. Pogrebnoi. (2015). Complex Hydrides Li2MH5 (M = B, Al) for Hydrogen Storage Application: Theoretical Study of Structure, Vibrational Spectra and Thermodynamic Properties. International Journal of Computational and Theoretical Chemistry, 3(6), 58-67. https://doi.org/10.11648/j.ijctc.20150306.13
ACS Style
Melkizedeck Hiiti Tsere; Tatiana P. Pogrebnaya; Alexander M. Pogrebnoi. Complex Hydrides Li2MH5 (M = B, Al) for Hydrogen Storage Application: Theoretical Study of Structure, Vibrational Spectra and Thermodynamic Properties. Int. J. Comput. Theor. Chem. 2015, 3(6), 58-67. doi: 10.11648/j.ijctc.20150306.13
AMA Style
Melkizedeck Hiiti Tsere, Tatiana P. Pogrebnaya, Alexander M. Pogrebnoi. Complex Hydrides Li2MH5 (M = B, Al) for Hydrogen Storage Application: Theoretical Study of Structure, Vibrational Spectra and Thermodynamic Properties. Int J Comput Theor Chem. 2015;3(6):58-67. doi: 10.11648/j.ijctc.20150306.13
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Download@article{10.11648/j.ijctc.20150306.13,
author = {Melkizedeck Hiiti Tsere and Tatiana P. Pogrebnaya and Alexander M. Pogrebnoi},
title = {Complex Hydrides Li2MH5 (M = B, Al) for Hydrogen Storage Application: Theoretical Study of Structure, Vibrational Spectra and Thermodynamic Properties},
journal = {International Journal of Computational and Theoretical Chemistry},
volume = {3},
number = {6},
pages = {58-67},
doi = {10.11648/j.ijctc.20150306.13},
url = {https://doi.org/10.11648/j.ijctc.20150306.13},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ijctc.20150306.13},
abstract = {Gaseous lithium complex hydrides Li2MH5 (M = B, Al) have been studied using DFT/B3P86 and MP2 methods with 6-311++G(d,p) basis set. High content of hydrogen by these materials accord them with good candidacy as a class of hydrogen storage materials. The optimized geometrical parameters, vibrational spectra and thermodynamic properties of the hydrides and the subunits LiH, Li2H+, Li2H2, MH3, MH4−, and LiMH4 have been determined. For the LiBH4 the equilibrium configuration was tridentate of C3v symmetry. For LiAlH4 two isomeric forms, bidentate (C2v) and tridentate (C3v), were confirmed to exist, and C2v isomer was shown to dominate in saturated vapor. For complex hydrides Li2MH5, different structural forms were considered but only one asymmetric form (C1) appeared to be equilibrium. Several possible channels of dissociation of Li2MH5 were considered; the enthalpies and Gibbs free energies of the reactions were computed. The enthalpies of formation ∆fH(0) of the complex hydrides in gaseous phase were determined: 60 ± 10 kJmol1 (Li2BH5) and 33 ± 10 kJmol1 (Li2AlH5). Heterophase decomposition of the gaseous Li2MH5 with solid products LiH and B/Al and hydrogen gas release was shown to be spontaneous at ambient temperature. Production of hydrogen gas via gaseous decomposition is highly endothermic and achievable at elevated temperatures. The complexes Li2MH5 are therefore proposed to be useful hydrogen storage materials under appropriate conditions.},
year = {2015}
}
TY - JOUR T1 - Complex Hydrides Li2MH5 (M = B, Al) for Hydrogen Storage Application: Theoretical Study of Structure, Vibrational Spectra and Thermodynamic Properties AU - Melkizedeck Hiiti Tsere AU - Tatiana P. Pogrebnaya AU - Alexander M. Pogrebnoi Y1 - 2015/12/18 PY - 2015 N1 - https://doi.org/10.11648/j.ijctc.20150306.13 DO - 10.11648/j.ijctc.20150306.13 T2 - International Journal of Computational and Theoretical Chemistry JF - International Journal of Computational and Theoretical Chemistry JO - International Journal of Computational and Theoretical Chemistry SP - 58 EP - 67 PB - Science Publishing Group SN - 2376-7308 UR - https://doi.org/10.11648/j.ijctc.20150306.13 AB - Gaseous lithium complex hydrides Li2MH5 (M = B, Al) have been studied using DFT/B3P86 and MP2 methods with 6-311++G(d,p) basis set. High content of hydrogen by these materials accord them with good candidacy as a class of hydrogen storage materials. The optimized geometrical parameters, vibrational spectra and thermodynamic properties of the hydrides and the subunits LiH, Li2H+, Li2H2, MH3, MH4−, and LiMH4 have been determined. For the LiBH4 the equilibrium configuration was tridentate of C3v symmetry. For LiAlH4 two isomeric forms, bidentate (C2v) and tridentate (C3v), were confirmed to exist, and C2v isomer was shown to dominate in saturated vapor. For complex hydrides Li2MH5, different structural forms were considered but only one asymmetric form (C1) appeared to be equilibrium. Several possible channels of dissociation of Li2MH5 were considered; the enthalpies and Gibbs free energies of the reactions were computed. The enthalpies of formation ∆fH(0) of the complex hydrides in gaseous phase were determined: 60 ± 10 kJmol1 (Li2BH5) and 33 ± 10 kJmol1 (Li2AlH5). Heterophase decomposition of the gaseous Li2MH5 with solid products LiH and B/Al and hydrogen gas release was shown to be spontaneous at ambient temperature. Production of hydrogen gas via gaseous decomposition is highly endothermic and achievable at elevated temperatures. The complexes Li2MH5 are therefore proposed to be useful hydrogen storage materials under appropriate conditions. VL - 3 IS - 6 ER -
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