Application of the aperiodic defect model to a negatively charged monovacancy in phosphorene

Abstract

We apply the recently introduced aperiodic defect model (ADM) to a negatively charged monovacancy in a phosphorene monolayer. In contrast to conventional supercell approaches, the ADM treats a single defect embedded in the true non-defective crystalline mean field, thereby avoiding spurious defect–defect interactions and the need for charge corrections. At the same time, it effectively reduces the calculation to a fragment, enabling the use of high-level molecular electronic-structure methods. Converging the Hartree–Fock and correlation contributions to the thermodynamic limit yields a benchmark CCSD(T)/POB-TZVP-rev2 formation energy of 0.81 eV for the negatively charged monovacancy in the (5|9) configuration. The excitation energy to the lowest singlet excited state of this defect at the EOM-CCSD/POB-TZVP-rev2 level is found to be 1.95 eV. Overall, the ADM provides a highly promising route toward quantitatively accurate and systematically improvable descriptions of defects in solids and on surfaces, bridging the gap between solid-state physics and molecular quantum chemistry.