Electronic and Vibrational Properties of gamma-AlH3

Physics – Condensed Matter – Materials Science

Scientific paper

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18 pages, 9 figures, submited to PRB

Scientific paper

10.1103/PhysRevB.77.014101

Aluminum hydride (alane) AlH_3 is an important material in hydrogen storage applications. It is known that AlH_3 exists in multiply forms of polymorphs, where $\alpha$-AlH_3 is found to be the most stable with a hexagonal structure. Recent experimental studies on $\gamma$-AlH_3 reported an orthorhombic structure with a unique double-bridge bond between certain Al and H atoms. This was not found in $\alpha$-AlH_3 or other polymorphs. Using density functional theory, we have investigated the energetics, and the structural, electronic, and phonon vibrational properties for the newly reported $\gamma$-AlH_3 structure. The current calculation concludes that $\gamma$-AlH_3 is less stable than $\alpha$-AlH_3 by 2.1 KJ/mol. Interesting binding features associated with the unique geometry of $\gamma$-AlH3 are discussed from the calculated electronic properties and phonon vibrational modes. The binding of H-s with higher energy Al-p,d orbitals is enhanced within the double-bridge arrangement, giving rise to a higher electronic energy for the system. Distinguishable new features in the vibrational spectrum of $\gamma$-AlH_3 were attributed to the double-bridge and hexagonal-ring structures.

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