In this Letter we develop a new systematic approach to study optical second harmonic generation in NiO, on both the (001) surface and the bulk. NiO is modeled as a doubly embedded cluster on which two highly correlated quantum chemistry methods are applied in order to obtain the wave functions of all the intragap $d$ states and the low lying charge transfer states. The optical gap is calculated and the electric dipole, magnetic dipole, and electric quadrupole contributions to the second order susceptibility tensor are computed for the first time from first principles. Going beyond the electric dipole approximation gives new insight into the experimentally observed spectrum. A method is proposed for monitoring the spin dynamics of the NiO(001) surface.

• Received 10 December 2004

DOI:https://doi.org/10.1103/PhysRevLett.95.077401