RESUMEN
Anhydrous sodium hydroxide, a common and structurally simple compound, shows spectacular isotope effects: NaOD undergoes a first-order transition, which is absent in NaOH. By combining ab initio electronic structure calculations with Feynman path integrals, we show that NaOH is an unusual example of a quantum paraelectric: zero-point quantum fluctuations stretch the weak hydrogen bonds (HBs) into a region where they are unstable and break. By strengthening the HBs via isotope substitution or applied pressure, the system can be driven to a broken-symmetry antiferroelectric phase. In passing, we provide a simple quantitative criterion for HB breaking in layered crystals and show that nuclear quantum effects are crucial in paraelectric to ferroelectric transitions in hydrogen-bonded hydroxides.
RESUMEN
Transport of hydrogen in hydrous minerals under high pressure is a key step for the water cycle within the Earth interior. Brucite Mg(OH)2 is one of the simplest minerals containing hydroxyl groups and is believed to decompose under the geological condition of the deep Earth's mantle. In the present study, we investigate the proton diffusion in brucite under high pressure, which results from a complex interplay between two processes: the O-H reorientations motion around the c axis and O-H covalent bond dissociations. First-principle path-integral molecular dynamics simulations reveal that the increasing pressure tends to lock the former motion, while, in contrast, it activates the latter which is mainly triggered by nuclear quantum effects. These two competing effects therefore give rise to a pressure sweet spot for proton diffusion within the mineral. In brucite Mg(OH)2, proton diffusion reaches a maximum for pressures close to 70GPa, while the structurally similar portlandite Ca(OH)2 never shows proton diffusion within the pressure range and time scale that we explored. We analyze the different behavior of brucite and portlandite, which might constitute two prototypes for other minerals with same structure.
RESUMEN
Gas hydrates consist of hydrogen-bonded water frameworks enclosing guest gas molecules and have been the focus of intense research for almost 40 y, both for their fundamental role in the understanding of hydrophobic interactions and for gas storage and energy-related applications. The stable structure of methane hydrate above 2 GPa, where CH4 molecules are located within H2O or D2O channels, is referred to as methane hydrate III (MH-III). The stability limit of MH-III and the existence of a new high-pressure phase above 40 to 50 GPa, although recently conjectured, remain unsolved to date. We report evidence for a further high-pressure, room-temperature phase of the CH4-D2O hydrate, based on Raman spectroscopy in diamond anvil cell and ab initio molecular dynamics simulations including nuclear quantum effects. Our results reveal that a methane hydrate IV (MH-IV) structure, where the D2O network is isomorphic with ice Ih, forms at â¼40 GPa and remains stable up to 150 GPa at least. Our proposed MH-IV structure is fully consistent with previous unresolved X-ray diffraction patterns at 55 GPa [T. Tanaka et al., J. Chem. Phys. 139, 104701 (2013)]. The MH-III â MH-IV transition mechanism, as suggested by the simulations, is complex. The MH-IV structure, where methane molecules intercalate the tetrahedral network of hexagonal ice, represents the highest-pressure gas hydrate known up to now. Repulsive interactions between methane and water dominate at the very high pressure probed here and the tetrahedral topology outperforms other possible arrangements in terms of space filling.