First principles study of hydrogen bond symmetrization in δ-AlOOH

Abstract

The high pressure behaviour of the hydrous mineral δ-AlOOH has been investigated by many experimental and theoretical studies, but the discrepancy in predicting the value of hydrogen symmetrization pressure was not resolved. Here, we investigated the high pressure behaviour of δ-AlOOH using first principles calculations and found that with proper optimization using pressure routine control, local density approximation (LDA) predicts the hydrogen symmetrization pressure as 15 GPa which is in good agreement with the experimentally predicted value which resolves the existing discrepancy and hence proving the validity of LDA in predicting the hydrogen symmetrization pressure. We further studied the compressibility behaviour of δ-AlOOH at low pressures and confirmed the P21nm to Pnnm transition of δ-AlOOH shown by the experimental work [Kuribayashi et al., Phys. Chem. Miner. 41, 303–312 (2014)]. We have also analysed the dependence of elastic constants, elastic moduli, sound velocities, and Raman spectrum of δ-AlOOH with pressure and found that a subtle change in the position of the hydrogen atom at hydrogen symmetrization pressure results into drastic changes in elastic and vibrational properties. Further, this study has been used to discuss the seismic anomalies observed in the upper mantle beneath the Deccan Volcanic Province in India and the Java subduction zone in the eastern flank of the Indian Ocean.