Understanding and calibrating Density-Functional-Theory calculations describing the energy and spectroscopy of defect sites in hexagonal boron nitride

TL;DR

This paper compares 13 computational methods to accurately characterize defect states in hexagonal boron nitride, addressing challenges in modeling excited states and spectral properties of defect sites in 2D materials.

Contribution

It systematically evaluates various DFT and ab initio methods for defect states in h-BN, providing insights into their accuracy and limitations for spectroscopic predictions.

Findings

Multi-reference effects significantly impact computational results.

DFT and TDDFT can yield differing excited state energies.

Nuclear relaxation influences spectral widths and defect stability.

Abstract

Defect states in 2D materials present many possible uses but both experimental and computational characterization of their spectroscopic properties is difficult. We provide and compare results from 13 DFT and ab initio computational methods for up to 25 excited states of a paradigm system, the VNCB defect in hexagonal boron nitride (h-BN). Studied include include: (i) potentially catastrophic effects for computational methods arising from the multi-reference nature of the closed-shell and open-shell states of the defect, which intrinsically involves broken chemical bonds, (ii) differing results from DFT and time-dependent DFT (TDDFT) calculations, (iii) comparison of cluster models to periodic-slab models of the defect, (iv) the starkly differing effects of nuclear relaxation on the various electronic states as broken bonds try to heal that control the widths of photoabsorption and photoemission spectra, (v) the effect of zero-point energy and entropy on free-energy differences, (vi) defect-localized and conduction/valence band transition natures, and (vii) strategies needed to ensure that the lowest-energy state of a defect can be computationally identified.