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Main Authors: Shen, Jiale, Liu, Haitao, Li, Yuanchang
Format: Preprint
Published: 2024
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Online Access:https://arxiv.org/abs/2406.06883
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author Shen, Jiale
Liu, Haitao
Li, Yuanchang
author_facet Shen, Jiale
Liu, Haitao
Li, Yuanchang
contents Gap opening remains elusive in copper chalcogenides (Cu$_{2}X$, $X$ = S, Se and Te), not least because Hubbard + $U$, hybrid functional and ${GW}$ methods have also failed. In this work, we elucidate that their failure originates from a severe underestimation of the 4$s$-3$d$ orbital splitting of the Cu atom, which leads to a band-order inversion in the presence of an anionic crystal field. As a result, the Fermi energy is pinned due to symmetry, yielding an invariant zero gap. Utilizing the hybrid pseudopotentials to correct the underestimation on the atomic side opens up gaps of experimental magnitude in Cu$_{2}X$, suggesting their predominantly electronic nature. Our work not only clarifies the debate about the Cu$_{2}X$ gap, but also provides a way to identify which of the different methods really captures the physical essence and which is the result of error cancellation.
format Preprint
id arxiv_https___arxiv_org_abs_2406_06883
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle A way to identify whether a DFT gap is from right reasons or error cancellations: The case of copper chalcogenides
Shen, Jiale
Liu, Haitao
Li, Yuanchang
Materials Science
Computational Physics
Gap opening remains elusive in copper chalcogenides (Cu$_{2}X$, $X$ = S, Se and Te), not least because Hubbard + $U$, hybrid functional and ${GW}$ methods have also failed. In this work, we elucidate that their failure originates from a severe underestimation of the 4$s$-3$d$ orbital splitting of the Cu atom, which leads to a band-order inversion in the presence of an anionic crystal field. As a result, the Fermi energy is pinned due to symmetry, yielding an invariant zero gap. Utilizing the hybrid pseudopotentials to correct the underestimation on the atomic side opens up gaps of experimental magnitude in Cu$_{2}X$, suggesting their predominantly electronic nature. Our work not only clarifies the debate about the Cu$_{2}X$ gap, but also provides a way to identify which of the different methods really captures the physical essence and which is the result of error cancellation.
title A way to identify whether a DFT gap is from right reasons or error cancellations: The case of copper chalcogenides
topic Materials Science
Computational Physics
url https://arxiv.org/abs/2406.06883