Electronic Structure of Cesium-based Photocathode Materials from Density Functional Theory: Performance of PBE, SCAN, and HSE06 functionals

TL;DR

This study evaluates the performance of PBE, SCAN, and HSE06 density functionals in predicting the electronic and structural properties of Cs-based photocathode materials, highlighting SCAN as the optimal balance of accuracy and efficiency.

Contribution

It systematically compares three density functionals for modeling Cs-based photocathode materials, identifying SCAN as the most effective for accurate and cost-efficient predictions.

Findings

PBE overestimates unit cell volume and underestimates band gap.

SCAN and HSE06 accurately reproduce structural and electronic properties.

Spin-orbit coupling effects are well captured by all functionals.

Abstract

The development of novel materials for vacuum electron sources in particle accelerators is an active field of research that can greatly benefit from the results of \textit{ab initio} calculations for the characterization of the electronic structure of target systems. As state-of-the-art many-body perturbation theory calculations are too expensive for large-scale material screening, density functional theory offers the best compromise between accuracy and computational feasibility. The quality of the obtained results, however, crucially depends on the choice of the exchange-correlation potential, $v_{xc}$. To address this essential point, we systematically analyze the performance of three popular approximations of $v_{xc}$ (PBE, SCAN, and HSE06) on the structural and electronic properties of bulk Cs$_3$Sb and Cs$_2$Te, two representative materials of Cs-based semiconductors employed in photocathode applications. Among the adopted approximations, PBE shows expectedly the largest discrepancies from the target: the unit cell volume is overestimated compared to the experimental value, while the band gap is severely underestimated. On the other hand, both SCAN and HSE06 perform remarkably well in reproducing both structural and electronic properties. Spin-orbit coupling, which mainly impacts the valence region of both materials inducing a band splitting and, consequently, a band-gap reduction of the order of 0.2 eV, is equally captured by all functionals. Our results indicate SCAN as the best trade-off between accuracy and computational costs, outperforming the considerably more expensive HSE06.