• electronic structure of metal hydrides;
  • alanes;
  • hydrogen storage;
  • cluster calculations;
  • density functional calculations


Quantum chemistry calculations are used to explore H2 loss from AlH3 and Al2 H6 and provide insight into the hydrogen production mechanism from polyalanes, a candidate material for energy storage. We present optimized structures for AlH3, Al2H4, Al2H5, and Al2H6 and some reaction pathways for their interconversion. We have found two pathways for the reaction Al2H6 → Al2H4 + H2, which have activation barriers lower in energy than for the removal of H2 from AlH3. However, the low-energy H2 loss pathway from Al2H6 suggests that the noninteracting Al–H bonds in the transition state structure favor having bonding similar to that occurring in AlH3. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010