Institute of Fundamental Technological Research

The path integral single sweep method is used to assess quantum effects on the free energy barrier for hydrogen vacancy diffusion in a defective Na3AlH6 crystal. This process has been investigated via experiments and simulations due to its potential relevance in the H release mechanism in sodium alanates, prototypical materials for solid state hydrogen storage. Previous computational studies, which used density functional methods for the electronic structure, were restricted to a classical treatment of the nuclear degrees of freedom. We show that, although they do not change the qualitative picture of the process, nuclear quantum effects reduce the free energy barrier height by about 18% with respect to the classical calculation improving agreement with available neutron scattering data.

Alanate, proton transfer, electron hopping, Car-Parrinello MD, molecular dynamics, Free Energy, Path Integral