Superconducting incommensurate host-guest phases in compressed elemental sulfur

TL;DR

This study predicts a novel incommensurate host-guest phase in compressed sulfur using DFT, revealing complex structural transitions and superconductivity with a peak T_c around 28 K at high pressure.

Contribution

First prediction of an incommensurate host-guest phase in elemental sulfur at high pressure, with detailed structural and superconducting properties.

Findings

Sulfur adopts a Barium-IVa type incommensurate host-guest phase between 386-679 GPa.

Chain rearrangements and atomic modulations stabilize the HG structure.

Superconducting T_c peaks between 24.8 and 28.2 K at 271 GPa.

Abstract

We use Density Functional Theory (DFT) and structure searching methods to show that the ground state of elemental sulfur is a Barium-IVa type incommensurate host-guest (HG) phase between $386$-$679$ GPa, becoming the first group-VI element predicted to possess such a structure. Within the HG phase, sulfur undergoes a series of transitions in which adjacent guest chains are not aligned but rather offset by different amounts, which can be described as a rearrangement of the stacking order of the chains. We show that these chain rearrangements are intimately coupled to modulations of the host and guest atoms which prove crucial to stabilising the HG structure. Unlike the high-pressure HG phases of other elements, sulfur does not exhibit interstitial charge localisation, and instead features strongly localised `voids' that are depleted of electronic charge. Prior to adopting the HG structure, we predict that sulfur possesses an orthorhombic structure of $Fdd2$ symmetry. We calculate the superconducting critical temperatures of these newly discovered phases, and show that $T_c$ is expected to peak between $24.8$ and $28.2$ K at $271$ GPa.