Density Functional Theory for 2D Transition-Metal Dichalcogenides with Extended Hubbard Parameters

Abstract

Accurate modelling of the band-edge electronic structure of transition metal dichalcogenides (TMDs), such as MoS$_2$, is essential for understanding their optical, electronic and spintronic properties and enabling future applications. Here, we supplement the standard PBE exchange-correlation functional with on-metal ($U$) and metal--chalcogen ($V$) Hubbard corrections, which can control the orbital composition of band-edge states and consequently improve the quantitative accuracy of various properties. For MoS$_2$, MoSe$_2$, WS$_2$, and WSe$_2$, we optimise the $U$ and $V$ parameters by comparison with experimentally measured spin--orbit splittings at the conduction and valence band edges, and show that these optimal choices also improve agreement of the computed band gap, and ferroelectric potential drop in rhombohedral bilayers, with experimentally measured values. This provides a highly efficient, scalable framework for quantitatively accurate, high-throughput calculations of monolayer and multilayer TMDs, suitable for implementation in 2D-materials databases, as well as large-scale electronic and spintronic device modelling.