The Electronic Structures and Energies of the Lowest Excited States of the Ns⁰, Ns⁺, Ns⁻ and Ns-H Defects in Diamond

This paper reports the energies and charge and spin distributions of the mono-substituted N defects, N⁰_s, N⁺_s, N⁻_s and N_s-H in diamonds from direct Δ-SCF calculations based on Gaussian orbitals within the B3LYP function. These predict that (i) N_s⁰, N_s⁺ and N_s⁻ all absorb in the region of the strong optical absorption at 270 nm (4.59 eV) reported by Khan et al., with the individual contributions dependent on the experimental conditions; (ii) N_s-H, or some other impurity, is responsible for the weak optical peak at 360 nm (3.44 eV); and that N_s⁺ is the source of the 520 nm (2.38 eV) absorption. All excitations below the absorption edge of the diamond host are predicted to be excitonic, with substantial re-distributions of charge and spin. The present calculations support the suggestion by Jones et al. that N_s⁺ contributes to, and in the absence of N_s⁰ is responsible for, the 4.59 eV optical absorption in N-doped diamonds. The semi-conductivity of the N-doped diamond is predicted to rise from a spin-flip thermal excitation of a CN hybrid orbital of the donor band resulting from multiple in-elastic phonon scattering. Calculations of the self-trapped exciton in the vicinity of N_s⁰ indicate that it is essentially a local defect consisting of an N and four nn C atoms, and that beyond these the host lattice is essential a pristine diamond as predicted by Ferrari et al. from the calculated EPR hyperfine constants.