Multiplet structure of chromium(III) dopants in wide band gap materials

TL;DR

This paper compares DFT and pEHCF methods for accurately modeling the electronic structure and excitations of chromium(III) dopants in wide band gap materials, aiding the design of advanced materials.

Contribution

It evaluates the effectiveness of DFT and pEHCF methods in describing the complex electronic states of chromium(III) in solid hosts, highlighting their strengths and limitations.

Findings

pEHCF better captures multi-reference excited states

DFT has limitations in describing $d$-$d$ excitations

Results support improved computational modeling of transition metal dopants

Abstract

Transition metal doping is commonly used for altering the properties of solid-state materials to suit applications in science and technology. Partially filled $d$-shells of transition metal atoms lead to electronic states with diverse spatial and spin symmetries. Chromium(III) cations have shown great potential for designing laser materials and, more recently, for developing spin qubits in quantum applications. They also represent an intriguing class of chemical systems with strongly correlated multi-reference excited states, due to the $d^3$ electron configuration. These states are difficult to describe accurately using single-reference quantum chemical methods such as density functional theory (DFT), the most commonly used method to study the electronic structures of solid-state systems. Recently, the periodic effective Hamiltonian of crystal field (pEHCF) method has been shown to overcome some limitations arising in the calculations of excited $d$-states. In this work, we assess the suitability of DFT and pEHCF to calculate the electronic structure and $d$-$d$ excitations of chromium(III) dopants in wide band gap host materials. The results will aid computational development of novel transition metal-doped materials and provide a deeper understanding of the complex nature of transition metal dopants in solids.