Orbital-Free Density Functional Theory Applied to NaAlH4

J. Phys. Chem. B, 109 (34), 16554 -16562, 2005. 10.1021/jp050191y S1089-5647(05)00191-4
Web Release Date: August 10, 2005

Orbital-Free Density Functional Theory Applied to NaAlH₄

Terry J. Frankcombe* and Geert-Jan Kroes

Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands

Nicholas I. Choly and Efthimios Kaxiras

Department of Physics and Division of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138

Received: January 11, 2005

In Final Form: July 8, 2005

Abstract:

We present the application of orbital-free density functional theory (OF-DFT) to NaAlH₄, a potential hydrogen storage material, and related systems. Although the simple Al and NaH structures are reproduced reasonably well by OF-DFT, the approach fails for the more complex NaAlH₄ structure. Calculations on AlH₃ show that the failure to describe the Al-H interaction is related to the kinetic energy functionals used rather than the local pseudopotentials which are required within the OF-DFT approach. Thus, systems such as NaAlH₄ present a challenge which awaits the development of more reliable orbital-free kinetic energy functionals.

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