Formation energies of silicon self-interstitials using periodic coupled cluster theory

Abstract

We present a study of the self-interstitial point defect formation energies in silicon using a range of quantum chemical theories, including the coupled cluster (CC) method within a periodic supercell approach. We study the formation energies of the X, T, H, and C3V self-interstitials and the vacancy V. Our results are compared to findings obtained using different ab initio methods published in the literature and partly to experimental data. In order to achieve computational results that are converged with respect to the system size and basis set, we employ the recently proposed finite-size error corrections and basis set incompleteness error corrections. Our coupled cluster with singles, doubles, and perturbative triples [CCSD(T)] calculations yield an order of stability of the X, H, and T self-interstitials, which agrees both with quantum Monte Carlo results and with predictions obtained using the random-phase approximation as well as using screened hybrid functionals. Compared to quantum Monte Carlo results with backflow corrections, the CCSD(T) formation energies of X and H are only slightly larger by about 100meV. However, in the case of the T self-interstitial, we find significant disagreement with all other theoretical predictions. Compared to quantum Monte Carlo calculations, CCSD(T) overestimates the formation energy of the T self-interstitial by 1.2eV. Although this can partly be attributed to strong correlation effects, more accurate electronic structure theories are needed to understand these findings.