First principles coupled cluster theory of the electronic spectrum of the transition metal dichalcogenides

TL;DR

This paper applies a high-level coupled cluster method to accurately compute the electronic bandgaps of monolayer transition metal dichalcogenides, providing benchmarks and insights into many-body effects in these 2D materials.

Contribution

It demonstrates the use of coupled cluster singles and doubles (CCSD) for 2D TMDs and compares results with GW simulations, highlighting strengths and limitations.

Findings

CCSD yields converged bandgaps consistent with GW but slightly higher.

CCSD predicts effective hole masses larger than previous reports.

Reasonable qualitative description of trion states, but poor excitation energies.

Abstract

The electronic properties of two-dimensional transition metal dichalcogenides (2D TMDs) have attracted much attention during the last decade. We show how a diagrammatic ab initio coupled cluster singles and doubles (CCSD) treatment paired with a careful thermodynamic limit extrapolation in two dimensions can be used to obtain converged bandgaps for monolayer materials in the MoS2 family. We find general agreement between CCSD and previously reported GW simulations in terms of the band structure, but predict slightly higher band gap values and effective hole masses compared to previous reports. We also investigate the ability of CCSD to describe trion states, finding reasonable qualitative structure, but poor excitation energies due to the lack of screening of three-particle excitations in the effective Hamiltonian. Our study provides an independent high-level benchmark of the role of many-body effects in 2D TMDs and showcases the potential strengths and weaknesses of diagrammatic coupled cluster approaches for realistic materials.