Effect of exchange-correlation and core-electron approximations on the calculated superconducting transition temperature of palladium hydride

TL;DR

This study investigates how different density functional theory schemes affect the predicted superconducting transition temperature of palladium hydride, revealing significant variability and highlighting the need for more advanced methods.

Contribution

It systematically evaluates the impact of exchange-correlation and core-electron approximations on Tc predictions within DFT, emphasizing the limitations of standard approaches.

Findings

Tc varies by over a factor of two across tested DFT schemes

Standard DFT approaches are unreliable for PdH Tc predictions

Higher-rung methods are needed for accurate lattice and phonon calculations

Abstract

Realistic prediction of the superconducting transition temperature (Tc) for PdH is a long-standing challenge, because it depends on robust calculations of the electron and phonon band structures to obtain the electron-phonon scattering matrix element. To date, first-principles calculations employing density functional theory (DFT) have been based on selected exchange-correlation and core-electron approximations. Incorporating anharmonicity produced a more realistic value of Tc that nevertheless still disagreed strongly with experiment unless adjustable parameters were introduced. Here we consider how the value of Tc predicted using DFT in the harmonic approximation depends on the DFT scheme employed. The rationale for this work is that unless the calculation of Tc within the harmonic approximation is robust, albeit incorrect, there is not a solid foundation for incorporating anharmonicity meaningfully. Six combinations of exchange-correlation approximation (LDA, PBE, PBEsol) and core-electron approximation (PAW, USPP) were tested. Following a carefully systematic methodology, the calculated Tc was found to vary by a factor exceeding two across the tested DFT schemes. This suggests strongly that "standard" DFT, even including anharmonicity, is not reliable for PdH, implying that a higher-rung method will be needed to calculate a realistic lattice constant and phonon band structure, and so predict Tc accurately.