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Abstract Studies of molecular mixtures containing hydrogen sulfide (H 2 S) could open up new routes towards hydrogen-rich high-temperature superconductors under pressure. H 2 S and ammonia (NH 3 ) form hydrogen-bonded molecular mixtures at ambient conditions, but their phase behavior and propensity towards mixing under pressure is not well understood. Here, we show stable phases in the H 2 S–NH 3 system under extreme pressure conditions to 4 Mbar from first-principles crystal structure prediction methods. We identify four stable compositions, two of which, (H 2 S) (NH 3 ) and (H 2 S) (NH 3 ) 4 , are stable in a sequence of structures to the Mbar regime. A re-entrant stabilization of (H 2 S) (NH 3 ) 4 above 300 GPa is driven by a marked reversal of sulfur-hydrogen chemistry. Several stable phases exhibit metallic character. Electron–phonon coupling calculations predict superconducting temperatures up to 50 K, in the Cmma phase of (H 2 S) (NH 3 ) at 150 GPa. The present findings shed light on how sulfur hydride bonding and superconductivity are affected in molecular mixtures. They also suggest a reservoir for hydrogen sulfide in the upper mantle regions of icy planets in a potentially metallic mixture, which could have implications for their magnetic field formation.
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Ammonia dimer: extremely fluxional but still hydrogen bonded
Abstract In the 1980s, Nelson, Fraser, and Klemperer (NFK) published an experimentally derived structure of the ammonia dimer dramatically different from the structure determined computationally, which led these authors to the question “Does ammonia hydrogen bond?. This question has not yet been answered satisfactorily. To answer it, we have developed an ab initio potential energy surface (PES) for this dimer at the limits of the current computational capabilities and performed essentially exact six-dimensional calculations of the vibration-rotation-tunneling (VRT) spectra of NH3-NH3and ND3-ND3, obtaining an unprecedented agreement with experimental spectra. In agreement with other recent electronic structure calculations, the global minimum on the PES is in a substantially bent hydrogen-bonded configuration. Since the bottom of the PES is exceptionally flat, the dimer is extremely fluxional and the probability of finding it in configurations that are not hydrogen bonded is high. Nevertheless, the probability of hydrogen-bonded configurations is large enough to consider the ammonia dimer to be hydrogen bonded. We also show that NFK’s inference that the ammonia dimer is nearly rigid actually results from unusual cancellations between quantum effects that generate differences in spectra of different isotopologues.
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- Award ID(s):
- 1900551
- PAR ID:
- 10363945
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 13
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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