Electron-phonon coupling and exchange-correlation effects in superconducting ${\rm H_3S}$ under high pressure

TL;DR

This study uses advanced density-functional theory calculations to show that the choice of exchange-correlation functional significantly affects the predicted superconducting transition temperature of high-pressure ${ m H_3S}$, highlighting the importance of methodological accuracy.

Contribution

It demonstrates that using the PBE0 hybrid functional increases the calculated $T_c$ by 25\% compared to PBE, emphasizing the impact of exchange-correlation effects on superconductivity predictions.

Findings

PBE0 enhances $T_c$ by 25\\% over PBE.

Exchange-correlation choice critically influences electron-phonon coupling calculations.

High-pressure equation of state and phonon frequencies are only slightly affected.

Abstract

We investigate the ${\rm H_3S}$ phase of sulphur hydride under high pressure $\simeq$ 200 GPa by means of {\it ab-initio} calculations within the framework of the density-functional theory (DFT) with the PBE0 hybrid exchange-correlation ($E_{\rm xc}$) approximation. The choice of $E_{\rm xc}$ has the largest effect on the calculated electron-phonon coupling (EPC) matrix elements; the high pressure equation of state and phonon frequencies are only slightly modified. Mode-dependent EPC correction factors are determined from PBE0 using a frozen-phonon supercell approach, while standard density-functional perturbation theory is used to determine the EPC with PBE generalized-gradient approximation $E_{\rm xc}$. Our principle finding is that the calculated PBE0 $T_c$ is enhanced by 25\% compared to PBE. This is similar in magnitude, but in opposite direction, to the proposed suppression of $T_c$ by anharmonic effects [Errea {\em et al., Phys. Rev. Lett.} {\bf 114}, 157004 (2015)]. Our calculations demonstrate the importance of considering exchange-correlation approximations for calculations of superconducting properties for this class of materials.