Dynamics and thermodynamics of a novel phase of NaAlH4.
We characterize a novel orthorhombic phase (gamma) of NaAlH4, discovered using first-principles molecular dynamics, and discuss its relevance to the dehydrogenation mechanism. This phase is close in energy to the known low-temperature structure and becomes the stabler phase above 320 K, thanks to a larger vibrational entropy associated with AlH4 rotational modes. The structural similarity of gamma-NaAlH4 to alpha-Na3AlH6 suggests it acts as a key intermediate during hydrogen release. Findings are consistent with recent experiments recording an unknown phase during dehydrogenation.
Wood
Brandon C
BC
Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Marzari
Nicola
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