Electronic structure of chromium trihalides beyond density functional theory

• Published in: Physical review. B 2021-10, Vol.104 (15), p.1, Article 155109
• Main Authors: Acharya, Swagata, Pashov, Dimitar, Cunningham, Brian, Rudenko, Alexander N., Rösner, Malte, Grüning, Myrta, van Schilfgaarde, Mark, Katsnelson, Mikhail I.
• Format: Article
• Language: English
• Subjects: Approximation; Bethe-Salpeter equation; Bromine; Chromium bromides; chromium compounds; CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Density functional theory; eigenvalues and eigenfunctions; Eigenvectors; Electronic structure; Electrons; Elementary excitations; Green's functions; GW method; Halogens; local density approximation; Mathematical analysis; monolayer films; monolayers; Perturbation; Valence band; valence bands
• ISSN: 2469-9950; 2469-9969
• DOI: 10.1103/PhysRevB.104.155109

We explore the electronic band structure of freestanding monolayers of chromium trihalides Cr X3, X = Cl, Br, I, within an advanced ab initio theoretical approach based on the use of Green's function functionals. We compare the local density approximation with the quasiparticle self-consistent GW (QSGW) approximation and its self-consistent extension (QS GˆW) by solving the particle-hole ladder Bethe-Salpeter equations to improve the effective interaction W. We show that, at all levels of theory, the valence band consistently changes shape in the sequence Cl → Br → I, and the valence band maximum shifts from the M point to the Γ point. By analyzing the dynamic and momentum-dependent self-energy, we show that QSGˆW adds to the localization of the systems in comparison with QSGW, thereby leading to a narrower band and reduced amount of halogens in the valence band manifold. Further analysis shows that X = Cl is most strongly correlated, and X = I is least correlated (most bandlike) as the hybridization between Cr d and X p enhances in the direction Cl → Br → I. For CrBr3 and CrI3, we observe remarkable differences between the QSGW and QSGˆW valence band structures, while their eigenfunctions are very similar. We show that weak perturbations, like moderate strain, weak changes to the d − p hybridization, and adding small U, can flip the valence band structures between these two solutions in these materials.