First-principles calculations have been performed on lithium borohydride $\mathrm{Li}\mathrm{B}{\mathrm{H}}_4$ using the ultrasoft pseudopotential method, which is a potential candidate for hydrogen storage materials due to its extremely large gravimetric capacity of $18\text{mass}\%$ hydrogen. We focus on an orthorhombic phase observed at ambient conditions and predict its fundamental properties; the structural properties, electronic properties, dielectric properties, vibrational properties, and the heat of formation. The calculation gives a nearly ideal tetrahedral shape for $\mathrm{B}{\mathrm{H}}_4$ complexes, although the recent experiment suggests that their configuration is strongly distorted [J-Ph. Soulié et al., J. Alloys Compd. 346, 200 (2002)]. Analyses for the electronic structure and the Born effective charge tensors indicate that Li atoms are ionized as ${\mathrm{Li}}^{+}$ cations. The internal bonding of ${\left[\mathrm{B}{\mathrm{H}}_4\right]}^{-}$ anions is primarily covalent. The high-frequency dielectric permittivity tensor ${\epsilon }_{\infty }$ is predicted as almost isotropic, but the static dielectric permittivity tensor ${\epsilon }_0$ as considerably anisotropic. The $\mathrm{\Gamma }$-phonon eigenmodes can be classified into three groups, namely, the librational modes involving the displacements of ${\mathrm{Li}}^{+}$ cations (less than $500{\mathrm{cm}}^{-1}$), and the internal B-H bending and stretching modes of ${\left[\mathrm{B}{\mathrm{H}}_4\right]}^{-}$ anions (around 1100 and $2300{\mathrm{cm}}^{-1}$, respectively). The molecular approximation fairly reproduces the phonon frequencies in the latter two groups, implying the strong internal bonding of $\mathrm{B}{\mathrm{H}}_4$ complexes. The librational modes have significant contributions to the large anisotropies of ${\epsilon }_0$. The agreement of the heat of formation with the experimental value is reasonably good.

• Received 27 January 2004

DOI:https://doi.org/10.1103/PhysRevB.69.245120