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Quantum hydrogen-bond symmetrization in the superconducting hydrogen sulfide system.

Accepted version
Peer-reviewed

Repository DOI


Type

Article

Change log

Authors

Errea, Ion 
Calandra, Matteo 
Pickard, Chris J 
Nelson, Joseph R 
Needs, Richard J 

Abstract

The quantum nature of the proton can crucially affect the structural and physical properties of hydrogen compounds. For example, in the high-pressure phases of H2O, quantum proton fluctuations lead to symmetrization of the hydrogen bond and reduce the boundary between asymmetric and symmetric structures in the phase diagram by 30 gigapascals (ref. 3). Here we show that an analogous quantum symmetrization occurs in the recently discovered sulfur hydride superconductor with a superconducting transition temperature Tc of 203 kelvin at 155 gigapascals--the highest Tc reported for any superconductor so far. Superconductivity occurs via the formation of a compound with chemical formula H3S (sulfur trihydride) with sulfur atoms arranged on a body-centred cubic lattice. If the hydrogen atoms are treated as classical particles, then for pressures greater than about 175 gigapascals they are predicted to sit exactly halfway between two sulfur atoms in a structure with Im3m symmetry. At lower pressures, the hydrogen atoms move to an off-centre position, forming a short H-S covalent bond and a longer H···S hydrogen bond in a structure with R3m symmetry. X-ray diffraction experiments confirm the H3S stoichiometry and the sulfur lattice sites, but were unable to discriminate between the two phases. Ab initio density-functional-theory calculations show that quantum nuclear motion lowers the symmetrization pressure by 72 gigapascals for H3S and by 60 gigapascals for D3S. Consequently, we predict that the Im3m phase dominates the pressure range within which the high Tc was measured. The observed pressure dependence of Tc is accurately reproduced in our calculations for the phase, but not for the R3m phase. Therefore, the quantum nature of the proton fundamentally changes the superconducting phase diagram of H3S.

Description

Keywords

cond-mat.supr-con, cond-mat.supr-con

Journal Title

Nature

Conference Name

Journal ISSN

0028-0836
1476-4687

Volume Title

532

Publisher

Springer Science and Business Media LLC
Sponsorship
Engineering and Physical Sciences Research Council (EP/J017639/1)
Engineering and Physical Sciences Research Council (EP/K014560/1)
We acknowledge financial support from the Spanish Ministry of Economy and Competitiveness (FIS2013- 48286-C2-2-P), French Agence Nationale de la Recherche (Grant No. ANR-13-IS10-0003- 392 01), EPSRC (UK) (Grant No. EP/J017639/1), Cambridge Commonwealth Trust, National Natural Science Foundation of China (Grants No. 11204111, 11404148, and 11274136), and 2012 Changjiang Scholars Program of China. Work at Carnegie was supported by EFree, an Energy Frontier Research Center funded by the DOE, Office of Science, Basic Energy Sciences under Award No. DE-SC-0001057. Computer facilities were provided by the PRACE project AESFT and the Donostia International Physics Center (DIPC).