Ab initio investigation of H-bond disordering in $δ$-AlOOH

Abstract

$δ$-AlOOH ($δ$) is a high-pressure hydrous phase that participates in the deep geological water cycle. At 0 GPa, $δ$ has asymmetric hydrogen bonds (H-bonds). Under pressure, it exhibits H-bond disordering, tunneling, and finally, H-bond symmetrization at ~18 GPa. This study investigates these 300 K pressure-induced state changes in $δ$ with ab initio calculations. H-bond disordering in $δ$ was modeled using supercell multi-configuration quasiharmonic calculations. We examine: (a) energy barriers for proton jumps, (b) the pressure dependence of phonon frequencies, (c) 300 K compressibility, (d) neutron diffraction pattern anomalies, and (e) compare ab initio bond lengths with measured ones. Such thorough and systematic comparisons indicate that: (a) proton "disorder" has a restricted meaning when applied to $δ$. Nevertheless, H-bonds are disordered between 0 and 8 GPa, and a gradual change in H-bond configuration results in enhanced compressibility. (b) several structural and vibrational anomalies at ~8 GPa are consistent with the disappearance of a particular (HOC-12) H-bond configuration and its change into another one (HOC-11*). (c) between 8-11 GPa, H-bond configuration (HOC-11*) is generally ordered, at least in short- to mid-range scale. (d) between 11.5-18 GPa, H-bond lengths approach a critical value that impedes compression, resulting in decreased compressibility. In this pressure range, especially approaching H-bond symmetrization at ~18 GPa, anharmonicity and tunneling should play an essential role in the proton dynamics. Further simulations accounting for these effects are desirable to clarify the protons' state in this pressure range.