Electronic Structure of Chromium Trihalides beyond Density Functional Theory

TL;DR

This study investigates the electronic band structure of monolayer chromium trihalides using advanced ab-initio methods, revealing how different theoretical approaches affect the predicted electronic properties and localization effects.

Contribution

It applies and compares multiple Green's function based ab-initio methods to analyze the electronic structure of chromium trihalides, highlighting the impact of higher-level theories on band characteristics.

Findings

Valence band shape changes across Cl, Br, I series.

Higher-level theories alter bandgap and eigenfunction details.

QS$Goxed{W}$ increases localization and narrows bands.

Abstract

We explore the electronic band structure of free standing monolayers of chromium trihalides, CrX\textsubscript{3}{, X= Cl, Br, I}, within an advanced \emph{ab-initio} theoretical approach based in the use of Green's function functionals. We compare the local density approximation with the quasi-particle self-consistent \emph{GW} approximation (QS\emph{GW}) and its self-consistent extension (QS$G\widehat{W}$) by solving the particle-hole ladder Bethe-Salpeter equations to improve the effective interaction \emph{W}. We show that at all levels of theory, the valence band consistently changes shape in the sequence Cl{\textrightarrow}Br{\textrightarrow}I, and the valence band maximum shifts from the M point to the $\Gamma$ point. However, the details of the transition, the one-particle bandgap, and the eigenfunctions change considerably going up the ladder to higher levels of theory. The eigenfunctions become more directional, and at the M point there is a strong anisotropy in the effective mass. Also the dynamic and momentum dependent self energy shows that QS$G\widehat{W}$ adds to the localization of the systems in comparison to the QS\emph{GW} thereby leading to a narrower band and reduced amount of halogens in the valence band manifold.