Time-disordered crystal structure of AlPO4-5

Modern ab initio calculations have become increasingly accurate for predicting the symmetry of crystal structures; however, the standard methods usually only determine the 0 K static configuration and therefore misrepresent structures where dynamics play a key role. In this work, we demonstrate a clear experimental example of this phenomenon in the AlPO4-5 molecular sieve where the average high-symmetry P6cc structure emerges from local dynamics involving corner-sharing tetrahedra. Quasielastic and inelastic neutron scattering experiments were conducted to clarify the thermally activated motions between 1.5 and 300 K. Through comparison with ab initio molecular dynamics, we explain why the theoretically predicted structure is not observed in diffraction experiments. Instead, the results indicate this material is an inorganic analogue of a plastic crystal where thermal dynamics dictate the average symmetry. © 2017 American Chemical Society

Keywords

Crystal structure, Oxygen, Multigroup theory, Molecular dynamics method, Energy, Symmetry, Neutron diffraction

Citation

Cortie, D. L., McBride, B. R., Narayanan, N., de Souza, N. R., Avdeev, M., Mole, R. A., McIntyre, G. J., Kearley, G. J., Withers, R., Yu, D. H., Liu, Y. (2017). Time-disordered crystal structure of AlPO4-5. The Journal of Physical Chemistry C, 121(34), 18762-18770. doi:10.1021/acs.jpcc.7b06415