The Electronic Structures and Energies of the Lowest Excited States of the N(s)(0), N(s)(+), N(s)(−) and N(s)-H Defects in Diamond

This paper reports the energies and charge and spin distributions of the mono-substituted N defects, N(0)(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(s)(0), 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(s)(0) 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(s)(0) 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.