A periodic equation-of-motion coupled-cluster implementation applied to $F$-centers in alkaline earth oxides

TL;DR

This paper develops a periodic boundary condition implementation of EOM-CCSD theory and applies it to study optical properties of $F$-centers in alkaline earth oxides, achieving good agreement with experimental data.

Contribution

The paper introduces a periodic boundary condition implementation of EOM-CCSD theory and applies it to $F$-centers in alkaline earth oxides, demonstrating its effectiveness for solid-state defect calculations.

Findings

EOM-CCSD predicts optical absorption energies accurately.

Extrapolation techniques improve convergence to the complete basis set limit.

Calculated emission energies align well with experimental observations.

Abstract

We present an implementation of equation of motion coupled-cluster singles and doubles (EOM-CCSD) theory using periodic boundary conditions and a plane wave basis set. Our implementation of EOM-CCSD theory is applied to study $F$-centers in alkaline earth oxides employing a periodic supercell approach. The convergence of calculated electronic excitation energies for neutral color centers in MgO, CaO and SrO crystals with respect to orbital basis set and system size is explored. We discuss extrapolation techniques that approximate excitation energies in the complete basis set limit and reduce finite size errors. Our findings demonstrate that EOM-CCSD theory can predict optical absorption energies of $F$-centers in good agreement with experiment. Furthermore, we discuss calculated emission energies corresponding to the decay from triplet to singlet states, responsible for the photoluminescence properties. Our findings are compared to experimental and theoretical results available in literature.