A theoretical study of high-pressure-induced phases of LiAlH4 using calculated NQCC parameters

Abstract

Quadrupolar parameters of nuclei can be used as a tool to understand the electronic structure of compounds. Lithium alanate (LiAlH4) is a potential hydrogen storage material because of its high capacity of 10.5 wt % H2. However, the drawbacks of its dehydrogenation process are the relatively high temperatures and the slow dehydrogenation kinetics; furthermore, its reversibility is rather poor. Understanding the bonding nature of Al and H is essential for improving its dehydrogenation performance. In this work the charge density distribution in LiAlH4 is studied. Thus using calculated nuclear quadrupole coupling constants of hydrogens (2H-NQCCs), the electronic structure of α-LiAlH4 with high pressure forms of LiAlH4, (β- and γ-LiAlH4) were compared. The results show that easier condition for dehydrogenation is expected in β-LiAlH4. Comparison of calculated dehydrogenation enthalpies of LiAlH4 phases verifies this prediction. The electric field gradient (EFG) of quadrupolar nuclei were calculated to obtain NQCC parameters. All calculations performed using Gaussian 03 at B3LYP/6-31G* level of theory.