High-temperature neutron diffraction study of deuterated brucite

To study the structural behavior of brucite at high temperature, we conducted in situ neutron diffraction experiments of a deuterated brucite powder sample, Mg(OD)₂, in the temperature range 313-583 K. The sample was stable up to 553 K, above which it started to decompose into periclase (MgO) and D₂O vapor. Rietveld analyses of the obtained data were performed using both single-site and three-site split-atom hydrogen models. Our results show that with increasing temperature, unit-cell parameter c increases at a rate ~7.7 times more rapidly than a. This large anisotropy of thermal expansion is primarily due to rapid increase in the interlayer thickness along the c-axis on heating. The amplitudes of thermal vibration for Mg, O, and D increase linearly with increasing temperature; however, the rate of the increase for the lighter D is much larger. In addition, D vibrates anisotropically with a higher magnitude within the (001) plane, as confirmed by our first-principles phonon calculations. On heating, the interatomic distances between a given D and its associated O and D from the adjacent [MgO₆] layer increase, whereas the O-D bond length decreases. This behavior suggests weakened D···O and D···D interlayer interactions but strengthened O-D bonding with increasing temperature.